ASTM D5453-19a

Standard Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence

SIGNIFICANCE AND USE
4.1 Some process catalysts used in petroleum and chemical refining can be poisoned when trace amounts of sulfur bearing materials are contained in the feedstocks. This test method can be used to determine sulfur in process feeds sulfur in finished products, and can also be used for purposes of regulatory control.
SCOPE
1.1 This test method covers the determination of total sulfur in liquid hydrocarbons, boiling in the range from approximately 25 °C to 400 °C, with viscosities between approximately 0.2 cSt and 20 cSt (mm2/s) at room temperature.  
1.2 Three separate interlaboratory studies (ILS) on precision, and three other investigations that resulted in an ASTM research report, have determined that this test method is applicable to naphthas, distillates, engine oil, ethanol, Fatty Acid Methyl Ester (FAME), and engine fuel such as gasoline, oxygen enriched gasoline (ethanol blends, E-85, M-85, RFG), diesel, biodiesel, diesel/biodiesel blends, and jet fuel. Samples containing 1.0 mg/kg to 8000 mg/kg total sulfur can be analyzed (Note 1).
Note 1: Estimates of the pooled limit of quantification (PLOQ) for the precision studies were calculated. Values ranged between less than 1.0 mg/kg and less than 5.0 mg/kg (see Section 9 and 16.1).  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use. For warning statements, see 3.1, 7.3, 7.4, Section 8, and 9.1.  
1.5 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Published
• Publication Date: 30-Jun-2019
• ICS: 75.100 - Lubricants, industrial oils and related products
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.03 - Elemental Analysis

Relations

• Replaces: ASTM D5453-19 - Standard Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence
• Effective Date: 01-Jul-2019
• Refers: ASTM D6299-23a - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Dec-2023
• Refers: ASTM D1250-19e1 - Standard Guide for the Use of the Joint API and ASTM Adjunct for Temperature and Pressure Volume Correction Factors for Generalized Crude Oils, Refined Products, and Lubricating Oils: API MPMS Chapter 11.1
• Effective Date: 01-May-2019
• Refers: ASTM D6299-17b - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Dec-2017
• Refers: ASTM D6299-17a - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Nov-2017
• Refers: ASTM D6299-17 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Jan-2017
• Refers: ASTM D6299-13e1 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Oct-2013
• Refers: ASTM D1298-12a - Standard Test Method for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method
• Effective Date: 15-May-2012
• Refers: ASTM D1298-12 - Standard Test Method for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method
• Effective Date: 01-Apr-2012
• Refers: ASTM D4057-06(2011) - Standard Practice for Manual Sampling of Petroleum and Petroleum Products
• Effective Date: 01-Jun-2011
• Refers: ASTM D6299-10 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Mar-2010
• Refers: ASTM D6299-10e2 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Mar-2010
• Refers: ASTM D6299-09 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Nov-2009
• Refers: ASTM D6299-08 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Oct-2008
• Refers: ASTM D6299-07e1 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Nov-2007

Overview

ASTM D5453-19a is a globally recognized standard for the accurate determination of total sulfur in light hydrocarbons, spark ignition engine fuel, diesel engine fuel, and engine oil using ultraviolet fluorescence detection. Developed by ASTM International, this test method serves a critical role in the petroleum and chemical industries by enabling precise analysis of sulfur content, which is essential for product quality control, catalyst protection, and meeting regulatory requirements.

This method is suitable for a broad range of liquid hydrocarbons that boil between approximately 25°C and 400°C and have viscosities from about 0.2 cSt to 20 cSt at room temperature. The method is applicable for sulfur concentrations typically ranging from 1.0 mg/kg up to 8000 mg/kg, making it highly versatile for both low-sulfur and high-sulfur samples.

Key Topics

• Total Sulfur Determination: Provides a standardized procedure for quantifying total sulfur in liquid hydrocarbons using high-temperature combustion and ultraviolet (UV) fluorescence detection.
• Applicable Sample Types: Covers naphthas, distillates, engine oils, ethanol, Fatty Acid Methyl Esters (FAME), gasoline (including ethanol blends like E-85 and M-85), diesel, biodiesel, diesel/biodiesel blends, and jet fuel.
• Sulfur Measurement Range: Enables accurate analysis in samples with sulfur levels from as low as 1 mg/kg to as high as 8000 mg/kg.
• Method Precision and Bias: Draws from multiple interlaboratory studies and research reports that assess repeatability, reproducibility, and possible method biases, ensuring reliable results across laboratories.
• Regulatory and Quality Applications: Supports compliance checks with environmental regulations and assures protection of refinery catalysts from sulfur poisoning.
• Sampling and Safety: Highlights best practices for sample collection, handling, and the establishment of safety, health, and environmental measures.
• Nitrogen Interference: Addresses potential test method interferences from nitrogen-containing compounds, particularly nitric oxide, which could bias sulfur results.
• Instrumentation: Utilizes specialized equipment such as combustion tubes, UV fluorescence detectors, microlitre syringes, and flow control systems to ensure measurement accuracy.

Applications

• Refinery and Chemical Plant Feedstock Analysis: Ensures that trace sulfur levels in process feeds are measured and controlled, protecting sensitive catalysts from poisoning and degradation.
• Fuel Quality Assurance: Widely used for certifying sulfur content in gasoline, diesel, biodiesel blends, and jet fuel, supporting the production of cleaner fuels and meeting stringent environmental standards.
• Regulatory Compliance: Provides reliable data for government reporting and compliance with sulfur limits set by regulatory agencies for fuels and lubricants.
• Product Development and Blending: Enables fuel producers and blenders to assess sulfur concentrations during product formulation and blending to achieve target specifications.
• Quality Control Laboratories: Used for routine and batch sample testing in commercial, governmental, and research laboratories to confirm product integrity and monitor for contamination.

Related Standards

• ASTM D4052 - Test Method for Density, Relative Density, and API Gravity of Liquids by Digital Density Meter
• ASTM D4057 - Practice for Manual Sampling of Petroleum and Petroleum Products
• ASTM D4177 - Practice for Automatic Sampling of Petroleum and Petroleum Products
• ASTM D1298 - Test Method for Density, Relative Density, or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method
• ASTM D6299 - Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• ASTM D1250 - Guide for Use of the Petroleum Measurement Tables

These related standards support the accurate implementation of ASTM D5453 by providing essential methods for sampling, density determination, and quality control, enhancing the reliability of sulfur analysis in liquid hydrocarbons.

---

Keywords: ASTM D5453, total sulfur determination, ultraviolet fluorescence, petroleum analysis, fuel sulfur content, diesel, gasoline, biodiesel, FAME, quality control, regulatory compliance, refinery catalyst protection.

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D5453 − 19a
Standard Test Method for
Determination of Total Sulfur in Light Hydrocarbons, Spark
Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by
Ultraviolet Fluorescence
This standard is issued under the fixed designation D5453; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* 2. Referenced Documents
2.1 ASTM Standards:
1.1 Thistestmethodcoversthedeterminationoftotalsulfur
D1250Guide for Use of the Petroleum MeasurementTables
in liquid hydrocarbons, boiling in the range from approxi-
D1298Test Method for Density, Relative Density, or API
mately 25°C to 400°C, with viscosities between approxi-
Gravity of Crude Petroleum and Liquid Petroleum Prod-
mately 0.2cSt and 20cSt (mm /s) at room temperature.
ucts by Hydrometer Method
1.2 Three separate interlaboratory studies (ILS) on
D4052Test Method for Density, Relative Density, and API
precision, and three other investigations that resulted in an
Gravity of Liquids by Digital Density Meter
ASTMresearchreport,havedeterminedthatthistestmethodis
D4057Practice for Manual Sampling of Petroleum and
applicable to naphthas, distillates, engine oil, ethanol, Fatty
Petroleum Products
Acid Methyl Ester (FAME), and engine fuel such as gasoline,
D4177Practice for Automatic Sampling of Petroleum and
oxygen enriched gasoline (ethanol blends, E-85, M-85, RFG),
Petroleum Products
diesel, biodiesel, diesel/biodiesel blends, and jet fuel. Samples
D6299Practice for Applying Statistical Quality Assurance
containing 1.0mg⁄kg to 8000mg⁄kg total sulfur can be ana-
and Control Charting Techniques to Evaluate Analytical
lyzed (Note 1).
Measurement System Performance
NOTE1—Estimatesofthepooledlimitofquantification(PLOQ)forthe
3. Summary of Test Method
precision studies were calculated. Values ranged between less than
1.0mg⁄kg and less than 5.0mg⁄kg (see Section 9 and 16.1). 3.1 A hydrocarbon sample is either directly injected or
placedinasampleboat.Thesampleorboat,orboth,isinserted
1.3 The values stated in SI units are to be regarded as
into a high temperature combustion tube where the sulfur is
standard. No other units of measurement are included in this
oxidizedtosulfurdioxide(SO )inanoxygenrichatmosphere.
standard.
Water produced during the sample combustion is removed and
1.4 This standard does not purport to address all of the
the sample combustion gases are next exposed to ultraviolet
safety concerns, if any, associated with its use. It is the
(UV) light.The SO absorbs the energy from the UVlight and
responsibility of the user of this standard to establish appro-
isconvertedtoexcitedsulfurdioxide(SO *).Thefluorescence
priate safety, health, and environmental practices and deter-
emitted from the excited SO * as it returns to a stable state,
mine the applicability of regulatory limitations prior to use.
SO , is detected by a photomultiplier tube and the resulting
For warning statements, see 3.1, 7.3, 7.4, Section 8, and 9.1.
signal is a measure of the sulfur contained in the sample.
1.5 This international standard was developed in accor- (Warning—Exposure to excessive quantities of ultraviolet
dance with internationally recognized principles on standard-
(UV) light is injurious to health. The operator must avoid
ization established in the Decision on Principles for the exposing any part of their person, especially their eyes, not
Development of International Standards, Guides and Recom-
only to direct UV light but also to secondary or scattered
mendations issued by the World Trade Organization Technical radiation that is present.)
Barriers to Trade (TBT) Committee.
4. Significance and Use
4.1 Some process catalysts used in petroleum and chemical
refining can be poisoned when trace amounts of sulfur bearing
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved July 1, 2019. Published August 2019. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 1993. Last previous edition approved in 2019 as D5453–19. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D5453-19A. the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5453 − 19a
FIG. 1 Conventional Combustion Tubes
materials are contained in the feedstocks.This test method can inlet end of the tube is large enough to accommodate a quartz
be used to determine sulfur in process feeds sulfur in finished sample boat.The combustion tube shall have one or more side
products, and can also be used for purposes of regulatory
arms for the introduction of oxygen and carrier gas or air. The
control.
oxidation section shall be large enough (see Fig. 1) to ensure
complete combustion of the sample. Fig. 1 depicts conven-
5. Interferences
tional combustion tubes. Other configurations are acceptable if
5.1 This test method is applicable for total sulfur determi-
precision is not degraded.
nation in liquid hydrocarbons containing less than 0.35%
6.3 Flow Control—The apparatus shall be equipped with a
(m ⁄m) halogen(s).
meansofflowcontrolthatiscapableofmaintainingaconstant
5.2 Nitric Oxide (NO) Interference—When in sufficient
supply of oxygen and carrier gas or air.
concentrations, bound nitrogen compounds present in the test
specimen, may cause sulfur results to be biased high for 6.4 Drier Tube—The apparatus must be equipped with a
apparatus types that do not account for the potential interfer-
mechanism for the removal of water vapor. The oxidation
ence. See AnnexA1 for instructions in determining if nitrogen
reaction produces water vapor which must be eliminated prior
interference is significant for a given apparatus or sulfur
tomeasurementbythedetector.Thiscanbeaccomplishedwith
determination application.
a membrane drying tube, or a permeation dryer, that utilizes a
selective capillary action for water removal.
6. Apparatus
6.5 UV Fluorescence Detector—Aqualitative and quantita-
6.1 Furnace—An electric furnace held at a temperature
tive detector capable of measuring light emitted from the
(1050°C min to 1150°C max) sufficient to pyrolyze all of the
fluorescence of sulfur dioxide by UV light.
sampleandoxidizesulfurtoSO .Theactualtemperaturetobe
recommended by the specific apparatus manufacturer.
6.6 Microlitre Syringe—Capable of accurately delivering
from5µLto90µLoftestspecimen.Checkwiththeinstrument
6.2 Combustion Tube—A quartz combustion tube con-
manufacturerforspecifictestspecimenvolumeandneedlesize
structed to allow the direct injection of the sample into the
heated oxidation zone of the furnace or constructed so that the requirements.
D5453 − 19a
FIG. 2 Direct Inject Syringe Drive
6.7 Sample Inlet System—Either of two types of sample 7. Reagents
inlet systems can be used.
7.1 Purity of Reagents—Reagent grade chemicals shall be
6.7.1 Direct Injection—Adirect injection inlet system must
used in tests. Unless otherwise indicated, it is intended that all
becapableofallowingthequantitativedeliveryofthematerial
reagents shall conform to the specifications of the Committee
to be analyzed into an inlet carrier stream which directs the
on Analytical Reagents of the American Chemical Society,
sample into the oxidation zone at a controlled and repeatable
where such specifications are available. Other grades may be
rate. A syringe drive mechanism which discharges the sample
used, provided it is first ascertained that the reagent is of
fromthemicrolitresyringeatarateofapproximately1µL⁄sis
sufficiently high purity to permit its use without lessening the
typical. Check with the instrument manufacturer for specific
accuracy of the determination.
test specimen injection rates. For example, see Fig. 2.
7.2 Carrier Gas—Inert gas or air. The actual gas to be
6.7.2 Boat Inlet System—An extended combustion tube
providesasealtotheinletoftheoxidationareaandissweptby recommended by the specific apparatus manufacturer.
a carrier gas. The system provides an area to position the
7.2.1 Inert Gas—Argon or helium only, high purity grade
sample carrying mechanism (boat) at a retracted position
(that is, chromatography or zero grade), 99.998% minimum
removed from the furnace. The boat drive mechanism will
purity, moisture 5mg⁄kg maximum.
fullyinserttheboatintothehottestsectionofthefurnaceinlet.
7.2.2 Air—High purity grade (that is, chromatography or
The sample boats and combustion tube are constructed of
zero grade), 99.99% minimum purity, moisture 5mg⁄kg
quartz. The combustion tube provides a cooling jacket for the
maximum.
area in which the retracted boat rests awaiting sample intro-
7.3 Oxygen (as required)—High purity (that is, chromatog-
duction from a microlitre syringe. A drive mechanism which
raphy or zero grade), 99.75% minimum purity, moisture
advances and withdraws the sample boat into and out of the
5 ppm w/w maximum, dried over molecular sieves.
furnace at a controlled and repeatable rate is required. For
(Warning—Vigorously accelerates combustion.)
example, see Fig. 3.
6.8 Refrigerated Circulator—An adjustable apparatus ca-
pableofdeliveringacoolantmaterialataconstanttemperature
Reagent Chemicals, American Chemical Society Specifications, American
as low as 4°C could be required when using the boat inlet
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
injection method (optional).
listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
6.9 Strip Chart Recorder, (optional).
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
6.10 Balance, with a precision of 60.01mg (optional). MD.
D5453 − 19a
FIG. 3 Boat Inlet System
7.4 Toluene, Xylenes, Isooctane, reagent grade (other sol- volume with selected solvent.This stock can be further diluted
vents similar to those occurring in samples to be analyzed are to desired sulfur concentration (Notes 4-7).
also acceptable). Correction for sulfur contribution from sol-
NOTE 4—Working standards that simulate or match the composition or
vents (solvent blank) used in standard preparation and sample
matrix of the samples analyzed can reduce test result bias between direct
specimen dilution is required. Alternatively, use of a solvent
inject and boat sample inlet systems.
withnondetectablelevelofsulfurcontaminationrelativetothe
NOTE 5—Working standards should be remixed on a regular basis
sulphur content in the sample unknown makes the blank
depending upon frequency of use and age.Typically, stock solutions have
correction unnecessary. (Warning—Flammable solvents.)
a useful life of about three months.
NOTE 6—Calibration standards can be prepared and diluted on a
7.5 Dibenzothiophene,FW184.26, 17.399% (m/m) S (Note
mass/mass basis when result calculations are adjusted to accommodate
2).
them.
7.6 Butyl Sulfide, FW146.29, 21.92% (m/m) S (Note 2).
NOTE7—Calibrationstandardsfromcommercialsourcescanbeusedif
checked for accuracy and if precision is not degraded.
7.7 Thionaphthene (Benzothiophene), FW134.20, 23.90%
(m/m) S (Note 2).
7.10 Quality Control (QC) Samples, preferably are portions
of one or more liquid petroleum materials that are stable and
NOTE 2—A correction for chemical impurity can be required.
representative of the samples of interest. These QC samples
7.8 Quartz Wool, or other suitable absorbent material that is
can be used to check the validity of the testing process as
stable and capable of withstanding temperatures inside the
described in Section 15.
furnace (see Note 3).
7.11 Oxidation Reagent (as required)—Tungsten trioxide
NOTE 3—Materials meeting the requirements in 7.8 provide a more
uniform injection of the sample into the boat by wicking any remaining (WO ), granular (typical particle size >2.0mm), high purity,
dropsofthesamplefromthetipofthesyringeneedlepriortointroduction
99.75% minimum.
of the sample into the furnace. Consult instrument manufacturer recom-
mendations for further guidance.
8. Hazards
7.9 Sulfur Stock Solution, 1000µg S/mL—Prepare a stock
8.1 Hightemperatureisemployedinthistestmethod.Extra
solution by accurately weighing approximately 0.5748g of
care must be exercised when using flammable materials near
dibenzothiophene or 0.4562g of butyl sulfide or 0.4184g of
thionaphthene into a tared 100mL volumetric flask. Dilute to the oxidative pyrolysis furnace.
D5453 − 19a
TABLE 1 Typical Operating Conditions
Syringe drive (direct inject) drive rate (700 to 750) 1 µL ⁄s
Boat drive (boat inlet) drive rate (700 to 750) 140 mm ⁄min to 160 mm ⁄min
Furnace temperature 1075 °C ± 25 °C
Furnace oxygen flowmeter setting (3.8 to 4.1) 450 mL ⁄min to 500 mL ⁄min
Inlet oxygen flowmeter setting (0.4 to 0.8) 10 mL ⁄min to 30 mL ⁄min
Inlet carrier flowmeter setting (3.4 to 3.6) 130 mL ⁄min to 160 mL ⁄min
TABLE 2 Typical Sulfur Calibration Ranges and Standard
9. Sampling
Concentrations
9.1 Obtain a test unit in accordance with Practice D4057 or
Curve I Curve II Curve III
Practice D4177. To preserve volatile components which are in
Sulfur, ng/µL Sulfur, ng/µL Sulfur, ng/µL
0.50 5.00 100.00
some samples, do not uncover samples any longer than
1.00 25.00 500.00
necessary. Samples shall be analyzed as soon as possible after
2.50 50.00 1000.00
taking from bulk supplies to prevent loss of sulfur or contami- 5.00 100.00
10.00
nation due to exposure or contact with sample container.
Injection Size Injection Size Injection Size
(Warning—Samples that are collected at temperatures below
10 µL to 20 µL 5 µL to 10 µL 5 µL
room temperature can undergo expansion and rupture the
container.Forsuchsamples,donotfillthecontainertothetop;
leave sufficient air space above the sample to allow room for
NOTE 10—Other injection sizes can be used when complete sample
expansion.)
combustion is not compromised and accuracy/precision are not degraded.
9.2 If the test unit is not used immediately, then thoroughly
11.3.1 The volumetric measurement of the injected material
mix in its container prior to taking a test specimen.
can be obtained by filling the syringe to the selected level.
Retract the plunger so that air is aspirated and the lower liquid
10. Preparation of Apparatus
meniscus falls on the 10% scale mark and record the volume
10.1 Assemble and leak check apparatus according to
of liquid in the syringe. After injection, again retract the
manufacturer’s instructions.
plunger so that the lower liquid meniscus falls on the 10%
10.2 Adjust the apparatus, depending upon the method of scale mark and record the volume of liquid in the syringe.The
sample introduction, to meet conditions described in Table 1. difference between the two volume readings is the volume of
sample injected (Note 11).
10.3 Adjust the instrument sensitivity and baseline stability
and perform instrument blanking procedures following manu-
NOTE 11—An automatic sampling and injection device can be used in
place of the described manual injection procedure.
facturer’s guidelines.
11.3.2 Fill the syringe as described in 11.3.1. Weigh the
11. Calibration and Standardization
device before and after injection to determine the amount of
11.1 Basedonanticipatedsulfurconcentration,selectoneof
sample injected. This procedure can provide greater accuracy
thesuggestedcurvesoutlinedinTable2.Narrowerrangesthan
than the volume delivery method, provided a balance with a
those indicated may be used, if desired. However, the test
precision of 60.01mg is used.
method precision using narrower ranges than those indicated
11.4 Once the appropriate sample size has been measured
have not been determined. Ensure the standards used for
into the microlitre syringe, promptly and quantitatively deliver
calibration bracket the concentrations of the samples being
the sample into the apparatus.Again, there are two alternative
analyzed. Carefully prepare a series of calibration standards
techniques available.
accordingly. Make other volumetric dilutions of the stock
11.4.1 For direct injection, carefully insert the syringe into
solution to cover the various ranges of operation within these
the inlet of the combustion tube and the syringe drive. Allow
calibrationcurveguidelines.Thenumberofstandardsusedper
time for sample residues to be burned from the needle (Needle
curve can vary, if equivalent results are obtained.
Blank).Onceastablebaselinehasreestablished,promptlystart
11.2 Flush the microlitre syringe several times with the
the analysis. Remove syringe once the apparatus has returned
sample prior to analysis. If bubbles are present in the liquid
to a stable baseline.
column, flush the syringe and withdraw a new sample.
11.4.2 For the boat inlet, quantitatively discharge the con-
tents of the syringe into the boat containing quartz wool or
11.3 A sample injection size recommended for the curve
suitable equivalent (see 7.8) at a slow rate being careful to
selected from Table 2 shall be quantitatively measured prior to
displace the last drop from the syringe needle. Remove the
injection into the combustion tube or delivery into the sample
syringe and promptly start the analysis. The instrument base-
boat for analysis (Notes 8-10). There are two alternative
line shall remain stable until the boat approaches the furnace
techniques available.
and vaporization of the sample begins. Instrument baseline is
NOTE 8—Injection of a constant or similar sample size for all materials
to be reestablished before the boat has been completely
analyzed in a selected operating range promotes consistent combustion
withdrawn from the furnace (Note 12). Once the boat has
conditions.
reached its fully retracted position, allow at least 1min for
NOTE 9—Injection of 10µLof the 100ng⁄µLstandard would establish
a calibration point equal to 1000ng or 1.0µg. cooling before the next sample injection (Note 12).
D5453 − 19a
NOTE12—Slowingboatspeedorbrieflypausingtheboatinthefurnace
12.3 Inspect the combustion tube and other flow path
can be necessary to ensure complete sample combustion. Direct injection
components to verify complete oxidation of the test specimen.
can ease sample handling and improve sample combustion characteristics
12.3.1 Direct Inject Systems—Reducethesamplesizeorthe
for materials containing very volatile sulfur compounds.
rate of injection, or both, of the specimen into the furnace if
11.4.3 The level of boat cooling required and the onset of
coke or sooting is observed.
sulfur detection following sample injection are directly related
12.3.2 Boat Inlet Systems—Increase the residence time for
to the volatility of the materials analyzed. For volatile
the boat in the furnace if coke or soot is observed on the boat.
materials, effective cooling of the sample boat prior to sample
Decrease the boat drive introduction rate or specimen sample
injection is essential. The use of a refrigerated circulator to
size, or both, if coke or soot is observed on the exit end of the
minimize the vaporization of the sample until the boat begins
combustion tube.
approaching the furnace or an increased time for boat cooling
12.3.3 Cleaning and Recalibration—Clean any coked or
can be required.
sooted parts per manufacturer’s instructions. After any clean-
ing or adjustment, assemble and leak check the apparatus.
11.5 Calibratetheinstrumentusingoneofthefollowingtwo
Repeat instrument calibration prior to reanalysis of the test
techniques.
specimen.
11.5.1 Perform measurements for the calibration standards
andblankusingoneoftheproceduresdescribedin11.2–11.4.
12.4 To obtain one result, measure each test specimen
Measure the calibration standards and blank three times.
solution three times and calculate the average detector re-
Subtracttheaverageresponseoftheblankinjectionsfromeach
sponses.
calibration standard response. Then determine the average
12.5 Determine density values (g/mL) needed for calcula-
integrated response of each concentration (see 7.4). Construct
tions by performing a gravimetric weighing of the test sample
a curve plotting of the average integrated detector response
intoaClassAvolumetricflask.SeeNote14.SeeSection13.1.
(y-axis) versus micrograms of sulfur injected (x-axis) (Note
13).Thiscurveshallbelinearandsystemperformancemustbe
NOTE 14—During the various interlaboratory studies (see 16.1), test
checked each day of use. See Section 15. sample density values (g/mL) needed for calculations were always
provided to participants and were determined by the ILS distributor in a
NOTE 13—Other calibration curve techniques can be used when
varietyofways;including,informationsuppliedbybulksamplesuppliers,
accuracy and precision are not degraded. accompanyinginformationfromdocumentationsuchassafetydatasheets
and gravimetric weighing into a volumetric flask at ambient laboratory
11.5.2 If the apparatus features self calibration routine,
temperatures, with the gravimetric method being the most common.
measure the calibration standards and blank three times using
12.5.1 Density values needed for calculations may be mea-
one of the procedures described in 11.2 – 11.4. If blank
sured using Test Methods D1298, D4052, or equivalent (see
correction is required and is not an available instrument option
Note 15).
(see 7.4 or 11.5.1), calibrate the analyzer in accordance with
manufacturer’s instructions to yield results expressed as nano-
NOTE 15—Users of the test method may convert density measured at
gramsofsulfur(Note13).Thiscurveshallbelinearandsystem standardtemperaturetothetemperatureatwhichthesamplewastestedby
using Guide D1250 and its adjuncts.
performance must be checked with each day of use (see
Section 15).
13. Calculation
11.6 If analyzer calibration is performed using a different
13.1 Calculate the density of the test sample in g/mL as
calibration curve than listed in Table 2, select an injection size
follows:
based on the curve closest in concentration to the measured
solution(s). Construct the calibration curve to yield values that Density ~g/mL!=M ⁄V (1)
d d
can be used to report sulfur content on a mass/mass basis.
where:
M = mass of sample (with a precision of 60.01mg), and
d
12. Procedure
V = volume of sample (with Class A precision).
d
12.1 Obtain a test specimen using the procedure described
13.2 For analyzers calibrated using a standard curve, calcu-
inSection9.Thesulfurconcentrationinthetestspecimenmust
late the sulfur content of the test specimen in parts per million
be less than the concentration of the highest standard and
(ppm) as follows:
greater than the concentration of the lowest standard used in
I 2 Y
~ !
the calibration. If required, a dilution can be performed on
Sulfur, ppm ~µg/g! 5 (2)
S 3 M 3 K
either a weight or volume basis. g
12.1.1 Gravimetric Dilution (mass/mass)—Record the mass
or,
ofthetestspecimenandthetotalmassofthetestspecimenand
~I 2 Y!~1000!
solvent.
Sulfur, ppm µg/g 5 (3)
~ !
S 3 V 3 K
v
12.1.2 Volumetric Dilution (mass/volume)—Record the
where:
mass of the test specimen and the total volume of the test
specimen and solvent.
D = density of test specimen solution, g/mL,
I = average of integrated detector response for test
12.2 Measure the response for the test specimen solution
specimen solution, counts,
using one of the procedures described in 11.2 – 11.4.
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D5453 − 19 D5453 − 19a
Standard Test Method for
Determination of Total Sulfur in Light Hydrocarbons, Spark
Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by
Ultraviolet Fluorescence
This standard is issued under the fixed designation D5453; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope*
1.1 This test method covers the determination of total sulfur in liquid hydrocarbons, boiling in the range from approximately
25 °C to 400 °C, with viscosities between approximately 0.2 cSt and 20 cSt (mm /s) at room temperature.
1.2 Three separate interlaboratory studies (ILS) on precision, and three other investigations that resulted in an ASTM research
report, have determined that this test method is applicable to naphthas, distillates, engine oil, ethanol, Fatty Acid Methyl Ester
(FAME), and engine fuel such as gasoline, oxygen enriched gasoline (ethanol blends, E-85, M-85, RFG), diesel, biodiesel,
diesel/biodiesel blends, and jet fuel. Samples containing 1.0 mg ⁄kg to 8000 mg ⁄kg total sulfur can be analyzed (Note 1).
NOTE 1—Estimates of the pooled limit of quantification (PLOQ) for the precision studies were calculated. Values ranged between less than 1.0 mg ⁄kg
and less than 5.05.0 mg mg/kg ⁄kg (see Section 89 and 15.116.1).
1.3 This test method is applicable for total sulfur determination in liquid hydrocarbons containing less than 0.35 % (m ⁄m)
halogen(s).
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of
regulatory limitations prior to use. For warning statements, see 3.1, 6.37.3, 6.47.4, Section 78, and 8.19.1.
1.5 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D1250 Guide for Use of the Petroleum Measurement Tables
D1298 Test Method for Density, Relative Density, or API Gravity of Crude Petroleum and Liquid Petroleum Products by
Hydrometer Method
D4052 Test Method for Density, Relative Density, and API Gravity of Liquids by Digital Density Meter
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
3. Summary of Test Method
3.1 A hydrocarbon sample is either directly injected or placed in a sample boat. The sample or boat, or both, is inserted into
a high temperature combustion tube where the sulfur is oxidized to sulfur dioxide (SO ) in an oxygen rich atmosphere. Water
produced during the sample combustion is removed and the sample combustion gases are next exposed to ultraviolet (UV) light.
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcommittee
D02.03 on Elemental Analysis.
Current edition approved May 1, 2019July 1, 2019. Published June 2019August 2019. Originally approved in 1993. Last previous edition approved in 20162019 as
ɛ1
D5453 – 16D5453 – 19. . DOI: 10.1520/D5453-19.10.1520/D5453-19A.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5453 − 19a
FIG. 1 Conventional Combustion Tubes
The SO absorbs the energy from the UV light and is converted to excited sulfur dioxide (SO *). The fluorescence emitted from
2 2
the excited SO * as it returns to a stable state, SO , is detected by a photomultiplier tube and the resulting signal is a measure of
2 2
the sulfur contained in the sample. (Warning—Exposure to excessive quantities of ultraviolet (UV) light is injurious to health. The
operator must avoid exposing any part of their person, especially their eyes, not only to direct UV light but also to secondary or
scattered radiation that is present.)
4. Significance and Use
4.1 Some process catalysts used in petroleum and chemical refining can be poisoned when trace amounts of sulfur bearing
materials are contained in the feedstocks. This test method can be used to determine sulfur in process feeds sulfur in finished
products, and can also be used for purposes of regulatory control.
5. Interferences
5.1 This test method is applicable for total sulfur determination in liquid hydrocarbons containing less than 0.35 %
(m ⁄m) halogen(s).
5.2 Nitric Oxide (NO) Interference—When in sufficient concentrations, bound nitrogen compounds present in the test specimen,
may cause sulfur results to be biased high for apparatus types that do not account for the potential interference. See Annex A1 for
instructions in determining if nitrogen interference is significant for a given apparatus or sulfur determination application.
6. Apparatus
6.1 Furnace—An electric furnace held at a temperature (1050 °C min to 1150 °C max) sufficient to pyrolyze all of the sample
and oxidize sulfur to SO . The actual temperature to be recommended by the specific apparatus manufacturer.
6.2 Combustion Tube—A quartz combustion tube constructed to allow the direct injection of the sample into the heated
oxidation zone of the furnace or constructed so that the inlet end of the tube is large enough to accommodate a quartz sample boat.
The combustion tube shall have one or more side arms for the introduction of oxygen and carrier gas or air. The oxidation section
shall be large enough (see Fig. 1) to ensure complete combustion of the sample. Fig. 1 depicts conventional combustion tubes.
D5453 − 19a
FIG. 2 Direct Inject Syringe Drive
Other configurations are acceptable if precision is not degraded.
6.3 Flow Control—The apparatus shall be equipped with a means of flow control that is capable of maintaining a constant
supply of oxygen and carrier gas or air.
6.4 Drier Tube—The apparatus must be equipped with a mechanism for the removal of water vapor. The oxidation reaction
produces water vapor which must be eliminated prior to measurement by the detector. This can be accomplished with a membrane
drying tube, or a permeation dryer, that utilizes a selective capillary action for water removal.
6.5 UV Fluorescence Detector—A qualitative and quantitative detector capable of measuring light emitted from the fluorescence
of sulfur dioxide by UV light.
6.6 Microlitre Syringe—Capable of accurately delivering from 5 μL to 90 μL of test specimen. Check with the instrument
manufacturer for specific test specimen volume and needle size requirements.
6.7 Sample Inlet System—Either of two types of sample inlet systems can be used.
6.7.1 Direct Injection—A direct injection inlet system must be capable of allowing the quantitative delivery of the material to
be analyzed into an inlet carrier stream which directs the sample into the oxidation zone at a controlled and repeatable rate. A
syringe drive mechanism which discharges the sample from the microlitre syringe at a rate of approximately 11 μL μL/s ⁄s is
typical. Check with the instrument manufacturer for specific test specimen injection rates. For example, see Fig. 2.
6.7.2 Boat Inlet System—An extended combustion tube provides a seal to the inlet of the oxidation area and is swept by a carrier
gas. The system provides an area to position the sample carrying mechanism (boat) at a retracted position removed from the
furnace. The boat drive mechanism will fully insert the boat into the hottest section of the furnace inlet. The sample boats and
combustion tube are constructed of quartz. The combustion tube provides a cooling jacket for the area in which the retracted boat
rests awaiting sample introduction from a microlitre syringe. A drive mechanism which advances and withdraws the sample boat
into and out of the furnace at a controlled and repeatable rate is required. For example, see Fig. 3.
6.8 Refrigerated Circulator—An adjustable apparatus capable of delivering a coolant material at a constant temperature as low
as 4 °C could be required when using the boat inlet injection method (optional).
6.9 Strip Chart Recorder, (optional).
6.10 Balance, with a precision of 60.01 mg (optional).
D5453 − 19a
FIG. 3 Boat Inlet System
7. Reagents
7.1 Purity of Reagents—Reagent grade chemicals shall be used in tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
7.2 Carrier Gas—Inert gas or air. The actual gas to be recommended by the specific apparatus manufacturer.
7.2.1 Inert Gas—Argon or helium only, high purity grade (that is, chromatography or zero grade), 99.998 % minimum purity,
moisture 5 mg ⁄kg maximum.
7.2.2 Air—High purity grade (that is, chromatography or zero grade), 99.99 % minimum purity, moisture 5 mg ⁄kg maximum.
7.3 Oxygen (as required)—High purity (that is, chromatography or zero grade), 99.75 % minimum purity, moisture 5 ppm
5 ppm w/w maximum, dried over molecular sieves. (Warning—Vigorously accelerates combustion.)
7.4 Toluene, Xylenes, Isooctane, reagent grade (other solvents similar to those occurring in samples to be analyzed are also
acceptable). Correction for sulfur contribution from solvents (solvent blank) used in standard preparation and sample specimen
dilution is required. Alternatively, use of a solvent with nondetectable level of sulfur contamination relative to the sulphur content
in the sample unknown makes the blank correction unnecessary. (Warning—Flammable solvents.)
7.5 Dibenzothiophene, FW184.26, 17.399 % (m/m) S (Note 2).
7.6 Butyl Sulfide, FW146.29, 21.92 % (m/m) S (Note 2).
7.7 Thionaphthene (Benzothiophene), FW134.20, 23.90 % (m/m) S (Note 2).
NOTE 2—A correction for chemical impurity can be required.
7.8 Quartz Wool, or other suitable absorbent material that is stable and capable of withstanding temperatures inside the furnace
(see Note 3).
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 Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
D5453 − 19a
TABLE 1 Typical Operating Conditions
Syringe drive (direct inject) drive rate (700–750) 1 μL/s
Syringe drive (direct inject) drive rate (700 to 750) 1 μL ⁄s
Boat drive (boat inlet) drive rate (700–750) 140 mm/min – 160 mm/min
Boat drive (boat inlet) drive rate (700 to 750) 140 mm ⁄min to 160 mm ⁄min
Furnace temperature 1075 °C ± 25 °C
Furnace oxygen flowmeter setting (3.8–4.1) 450 mL ⁄min –500 mL/min
Furnace oxygen flowmeter setting (3.8 to 4.1) 450 mL ⁄min to 500 mL ⁄min
Inlet oxygen flowmeter setting (0.4–0.8) 10 mL ⁄min –30 mL/min
Inlet oxygen flowmeter setting (0.4 to 0.8) 10 mL ⁄min to 30 mL ⁄min
Inlet carrier flowmeter setting (3.4–3.6) 130 mL ⁄min –160 mL/min
Inlet carrier flowmeter setting (3.4 to 3.6) 130 mL ⁄min to 160 mL ⁄min
NOTE 3—Materials meeting the requirements in 6.87.8 provide a more uniform injection of the sample into the boat by wicking any remaining drops
of the sample from the tip of the syringe needle prior to introduction of the sample into the furnace. Consult instrument manufacturer recommendations
for further guidance.
7.9 Sulfur Stock Solution, 1000 μg S/mL—Prepare a stock solution by accurately weighing approximately 0.5748 g of
dibenzothiophene or 0.4562 g of butyl sulfide or 0.4184 g of thionaphthene into a tared 100 mL volumetric flask. Dilute to volume
with selected solvent. This stock can be further diluted to desired sulfur concentration (Notes 4-7).
NOTE 4—Working standards that simulate or match the composition or matrix of the samples analyzed can reduce test result bias between direct inject
and boat sample inlet systems.
NOTE 5—Working standards should be remixed on a regular basis depending upon frequency of use and age. Typically, stock solutions have a useful
life of about three months.
NOTE 6—Calibration standards can be prepared and diluted on a mass/mass basis when result calculations are adjusted to accommodate them.
NOTE 7—Calibration standards from commercial sources can be used if checked for accuracy and if precision is not degraded.
7.10 Quality Control (QC) Samples, preferably are portions of one or more liquid petroleum materials that are stable and
representative of the samples of interest. These QC samples can be used to check the validity of the testing process as described
in Section 1415.
7.11 Oxidation Reagent (as required)—Tungsten trioxide (WO ), granular (typical particle size >2.0 mm), high purity, 99.75 %
minimum.
8. Hazards
8.1 High temperature is employed in this test method. Extra care must be exercised when using flammable materials near the
oxidative pyrolysis furnace.
9. Sampling
9.1 Obtain a test unit in accordance with Practice D4057 or Practice D4177. To preserve volatile components which are in some
samples, do not uncover samples any longer than necessary. Samples shall be analyzed as soon as possible after taking from bulk
supplies to prevent loss of sulfur or contamination due to exposure or contact with sample container. (Warning—Samples that are
collected at temperatures below room temperature can undergo expansion and rupture the container. For such samples, do not fill
the container to the top; leave sufficient air space above the sample to allow room for expansion.)
9.2 If the test unit is not used immediately, then thoroughly mix in its container prior to taking a test specimen.
10. Preparation of Apparatus
10.1 Assemble and leak check apparatus according to manufacturer’s instructions.
10.2 Adjust the apparatus, depending upon the method of sample introduction, to meet conditions described in Table 1.
10.3 Adjust the instrument sensitivity and baseline stability and perform instrument blanking procedures following manufac-
turer’s guidelines.
11. Calibration and Standardization
11.1 Based on anticipated sulfur concentration, select one of the suggested curves outlined in Table 2. Narrower ranges than
those indicated may be used, if desired. However, the test method precision using narrower ranges than those indicated have not
been determined. Ensure the standards used for calibration bracket the concentrations of the samples being analyzed. Carefully
prepare a series of calibration standards accordingly. Make other volumetric dilutions of the stock solution to cover the various
ranges of operation within these calibration curve guidelines. The number of standards used per curve can vary, if equivalent results
are obtained.
11.2 Flush the microlitre syringe several times with the sample prior to analysis. If bubbles are present in the liquid column,
flush the syringe and withdraw a new sample.
D5453 − 19a
TABLE 2 Typical Sulfur Calibration Ranges and Standard
Concentrations
Curve I Curve II Curve III
Sulfur, ng/μL Sulfur, ng/μL Sulfur, ng/μL
0.50 5.00 100.00
1.00 25.00 500.00
2.50 50.00 1000.00
5.00 100.00
10.00
Injection Size Injection Size Injection Size
10 μL – 20 μL 5 μL – 10 μL 5 μL
10 μL to 20 μL 5 μL to 10 μL 5 μL
11.3 A sample injection size recommended for the curve selected from Table 2 shall be quantitatively measured prior to injection
into the combustion tube or delivery into the sample boat for analysis (Notes 8-10). There are two alternative techniques available.
NOTE 8—Injection of a constant or similar sample size for all materials analyzed in a selected operating range promotes consistent combustion
conditions.
NOTE 9—Injection of 10 μL of the 100 ng ⁄μL standard would establish a calibration point equal to 1000 ng or 1.0 μg.
NOTE 10—Other injection sizes can be used when complete sample combustion is not compromised and accuracy/precision are not degraded.
11.3.1 The volumetric measurement of the injected material can be obtained by filling the syringe to the selected level. Retract
the plunger so that air is aspirated and the lower liquid meniscus falls on the 10 % scale mark and record the volume of liquid in
the syringe. After injection, again retract the plunger so that the lower liquid meniscus falls on the 10 % scale mark and record
the volume of liquid in the syringe. The difference between the two volume readings is the volume of sample injected (Note 11).
NOTE 11—An automatic sampling and injection device can be used in place of the described manual injection procedure.
11.3.2 Fill the syringe as described in 10.3.111.3.1. Weigh the device before and after injection to determine the amount of
sample injected. This procedure can provide greater accuracy than the volume delivery method, provided a balance with a precision
of 60.01 mg is used.
11.4 Once the appropriate sample size has been measured into the microlitre syringe, promptly and quantitatively deliver the
sample into the apparatus. Again, there are two alternative techniques available.
11.4.1 For direct injection, carefully insert the syringe into the inlet of the combustion tube and the syringe drive. Allow time
for sample residues to be burned from the needle (Needle Blank). Once a stable baseline has reestablished, promptly start the
analysis. Remove syringe once the apparatus has returned to a stable baseline.
11.4.2 For the boat inlet, quantitatively discharge the contents of the syringe into the boat containing quartz wool or suitable
equivalent (see 6.87.8) at a slow rate being careful to displace the last drop from the syringe needle. Remove the syringe and
promptly start the analysis. The instrument baseline shall remain stable until the boat approaches the furnace and vaporization of
the sample begins. Instrument baseline is to be reestablished before the boat has been completely withdrawn from the furnace (Note
12). Once the boat has reached its fully retracted position, allow at least 1 min for cooling before the next sample injection (Note
12).
NOTE 12—Slowing boat speed or briefly pausing the boat in the furnace can be necessary to ensure complete sample combustion. Direct injection can
ease sample handling and improve sample combustion characteristics for materials containing very volatile sulfur compounds.
11.4.3 The level of boat cooling required and the onset of sulfur detection following sample injection are directly related to the
volatility of the materials analyzed. For volatile materials, effective cooling of the sample boat prior to sample injection is essential.
The use of a refrigerated circulator to minimize the vaporization of the sample until the boat begins approaching the furnace or
an increased time for boat cooling can be required.
11.5 Calibrate the instrument using one of the following two techniques.
11.5.1 Perform measurements for the calibration standards and blank using one of the procedures described in 10.211.2 –
10.411.4. Measure the calibration standards and blank three times. Subtract the average response of the blank injections from each
calibration standard response. Then determine the average integrated response of each concentration (see 6.47.4). Construct a curve
plotting of the average integrated detector response (y-axis) versus micrograms of sulfur injected (x-axis) (Note 13). This curve
shall be linear and system performance must be checked each day of use. See Section 1415.
NOTE 13—Other calibration curve techniques can be used when accuracy and precision are not degraded.
11.5.2 If the apparatus features self calibration routine, measure the calibration standards and blank three times using one of the
procedures described in 10.211.2 – 10.411.4. If blank correction is required and is not an available instrument option (see 6.47.4
or 10.5.111.5.1), calibrate the analyzer in accordance with manufacturer’s instructions to yield results expressed as nanograms of
sulfur (Note 13). This curve shall be linear and system performance must be checked with each day of use (see Section 1415).
D5453 − 19a
11.6 If analyzer calibration is performed using a different calibration curve than listed in Table 2, select an injection size based
on the curve closest in concentration to the measured solution(s). Construct the calibration curve to yield values that can be used
to report sulfur content on a mass/mass basis.
12. Procedure
12.1 Obtain a test specimen using the procedure described in Section 89. The sulfur concentration in the test specimen must be
less than the concentration of the highest standard and greater than the concentration of the lowest standard used in the calibration.
If required, a dilution can be performed on either a weight or volume basis.
12.1.1 Gravimetric Dilution (mass/mass)—Record the mass of the test specimen and the total mass of the test specimen and
solvent.
12.1.2 Volumetric Dilution (mass/volume)—Record the mass of the test specimen and the total volume of the test specimen and
solvent.
12.2 Measure the response for the test specimen solution using one of the procedures described in 10.211.2 – 10.411.4.
12.3 Inspect the combustion tube and other flow path components to verify complete oxidation of the test specimen.
12.3.1 Direct Inject Systems—Reduce the sample size or the rate of injection, or both, of the specimen into the furnace if coke
or sooting is observed.
12.3.2 Boat Inlet Systems—Increase the residence time for the boat in the furnace if coke or soot is observed on the boat.
Decrease the boat drive introduction rate or specimen sample size, or both, if coke or soot is observed on the exit end of the
combustion tube.
12.3.3 Cleaning and Recalibration—Clean any coked or sooted parts per manufacturer’s instructions. After any cleaning or
adjustment, assemble and leak check the apparatus. Repeat instrument calibration prior to reanalysis of the test specimen.
12.4 To obtain one result, measure each test specimen solution three times and calculate the average detector responses.
12.5 Determine density values (g/mL) needed for calculations by performing a gravimetric weighing of the test sample into a
Class A volumetric flask. See Note 14. See Section 12.113.1.
NOTE 14—During the various interlaboratory studies (see 15.116.1), test sample density values (g/mL) needed for calculations were always provided
to participants and were determined by the ILS distributor in a variety of ways; including, information supplied by bulk sample suppliers, accompanying
information from documentation such as safety data sheets and gravimetric weighing into a volumetric flask at ambient laboratory temperatures, with the
gravimetric method being the most common.
12.5.1 Density values needed for calculations may be measured using Test Methods D1298, D4052, or equivalent (see Note 15).
NOTE 15—Users of the test method may convert density measured at standard temperature to the temperature at which the sample was tested by using
Guide D1250 and its adjuncts.
13. Calculation
13.1 Calculate the density of the test sample in g/mL as follows:
Density ~g/mL! =M ⁄V (1)
d d
where:
M = mass of sample (with a precision of 60.01 mg), and
d
M = mass of sample (with a precision of 60.01 mg), and
d
V = volume of sample (with Class A precision).
d
13.2 For analyzers calibrated using a standard curve, calculate the sulfur content of the test specimen in parts per million (ppm)
as follows:
I 2 Y
~ !
Sulfur, ppm µg/g 5 (2)
~ !
S 3M 3K
g
or,
I 2 Y 1000
~ ! ~ !
Sulfur, ppm ~µg/g!5 (3)
S 3V 3K
v
where:
D = density of test specimen solution, g/mL,
I = average of integrated detector response for test specimen solution, counts,
K = gravimetric dilution factor, mass of test specimen/mass of test specimen and solvent, g/g,
g
K = volumetric dilution factor, mass of test specimen/volume of test specimen and solvent, g/mL,
v
M = mass of test specimen
...