ASTM D7359-08
(Test Method)Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatography Detection (Combustion Ion Chromatography-CIC)
Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatography Detection (Combustion Ion Chromatography-CIC)
SIGNIFICANCE AND USE
The total fluorine, chlorine and sulfur contained in aromatic hydrocarbon matrices can contribute to emissions, be harmful to many catalytic chemical processes, and lead to corrosion. This test method can be used to determine total sulfur and halogens aromatic hydrocarbon matrices, in finished products and can be used for compliance determinations when acceptable to a regulatory authority using performance based criteria.
SCOPE
1.1 This test method covers the individual determination of total fluorine, chlorine and sulfur in aromatic hydrocarbons and their mixtures. Samples containing 0.1 to 50 mg/kg of each element can be analyzed.
1.2 This method can be applied to sample types outside the range of the scope by dilution of the sample in an appropriate solvent to bring the total concentrations of fluorine, chlorine and sulfur within the range covered by the test method. However, it is the responsibility of the analyst to verify the solubility of the sample in the solvent and that the diluted sample results conform to the precision and accuracy of the method.
1.3 In determining the conformance of the test results using this method to applicable specifications, results shall be rounded off in accordance with the rounding-off method of Practice E 29.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 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 and health practices and determine the applicability of regulatory limitations prior to use. See Section 8.
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Designation: D7359 − 08
StandardTest Method for
Total Fluorine, Chlorine and Sulfur in Aromatic
Hydrocarbons and Their Mixtures by Oxidative
Pyrohydrolytic Combustion followed by Ion
Chromatography Detection (Combustion Ion
Chromatography-CIC)
This standard is issued under the fixed designation D7359; 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 D6809 Guide for Quality Control and Quality Assurance
Procedures for Aromatic Hydrocarbons and Related Ma-
1.1 This test method covers the individual determination of
terials
totalfluorine,chlorineandsulfurinaromatichydrocarbonsand
E29 Practice for Using Significant Digits in Test Data to
their mixtures. Samples containing 0.1 to 50 mg/kg of each
Determine Conformance with Specifications
element can be analyzed.
2.2 Other Documents:
1.2 This method can be applied to sample types outside the
OSHA Regulations, 29 CFR paragraphs 1910.1000 and
range of the scope by dilution of the sample in an appropriate
1910.1200
solvent to bring the total concentrations of fluorine, chlorine
and sulfur within the range covered by the test method.
3. Summary of Test Method
However, it is the responsibility of the analyst to verify the
3.1 A sample of known weight or volume is placed into a
solubility of the sample in the solvent and that the diluted
sample boat and introduced at a controlled rate into a high
sample results conform to the precision and accuracy of the
temperature combustion tube. There the sample is combusted
method.
in an oxygen rich pyrohydrolytic environment. The gaseous
1.3 In determining the conformance of the test results using
by-products of the combusted sample are trapped in an
this method to applicable specifications, results shall be
absorption medium where the hydrogen halides (HX) formed
rounded off in accordance with the rounding-off method of -
during combustion disassociate into their respective ions, X
Practice E29.
while the sulfur oxides (SO ) formed are further oxidized to
X
2-
1.4 The values stated in SI units are to be regarded as
SO in the presence of an oxidizing agent. An aliquot of
standard. No other units of measurement are included in this known volume of the adsorbing solution is then automatically
standard. injected into an ion chromatograph (IC) by means of a sample
injectionvalve.Thehalideandsulfateanionsareseparatedinto
1.5 This standard does not purport to address all of the
individualelutionbandsontheseparatorcolumnoftheIC.The
safety concerns, if any, associated with its use. It is the
conductivity of the eluent is reduced with an anion suppression
responsibility of the user of this standard to establish appro-
device prior to the ion chromatograph’s thermal conductivity
priate safety and health practices and determine the applica-
detector, where the anions of interest are measured. Quantifi-
bility of regulatory limitations prior to use. See Section 8.
cation of the fluorine, chlorine and sulfur in the original
2. Referenced Documents
combusted sample is achieved by first calibrating the system
with a series of standards containing known amounts of
2.1 ASTM Standards:
fluorine, chlorine and sulfur and then analyzing unknown
D1193 Specification for Reagent Water
samples under the same conditions as the standards. The
combined system of pyrohydrolytic combustion followed by
This test method is under the jurisdiction of ASTM Committee D16 on
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of
ionchromatographicdetectionisreferredtoasCombustionIon
Subcommittee D16.04 on Instrumental Analysis.
Chromatography (CIC).
Current edition approved Oct. 15, 2008. Published November 2008. DOI:
10.1520/D7359-08.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
Standards volume information, refer to the standard’s Document Summary page on 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http://
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D7359 − 08
4. Significance and Use bustion by-products (HX and SO2) are absorbed. The Gas
Adsorption Unit rinses the gas lines and adsorption tube with
4.1 The total fluorine, chlorine and sulfur contained in
TypeIreagentwater(7.2)priortosamplecombustionandafter
aromatic hydrocarbon matrices can contribute to emissions, be
the absorption solution is injected into the Ion Chromatograph
harmful to many catalytic chemical processes, and lead to
to minimize cross contamination from the previous analysis.
corrosion. This test method can be used to determine total
sulfur and halogens aromatic hydrocarbon matrices, in finished 6.8 Gas-Tight Sampling Syringe, capable of accurately de-
products and can be used for compliance determinations when
livering 10 to 80 µL of standard or sample.
acceptable to a regulatory authority using performance based
6.9 Pyrohydrolytic Combustion Tube made of quartz and
criteria.
constructed such that when the sample is combusted in the
presence of humidified oxygen, the by-products of combustion
5. Interferences
are swept into the humidified pyrohydrolytic combustion zone.
5.1 Substances that co-elute with the anions of interest will
The inlet end shall allow for the stepwise introduction and
interfere. A high concentration of one anion can interfere with
advancement of a sample boat into the heated zone and shall
other constituents if their retention times are close enough to
have a side arm for the introduction of the humidified carrier
affect the resolution of their peak.
gas and oxygen. The pyrohydrolytic combustion tube must be
of ample volume, and have a heated zone with quartz wool or
6. Apparatus
other suitable medium providing sufficient surface area so that
6.1 Autosampler (Optional), capable of accurately deliver-
the complete pyrohydrolytic combustion of the sample is
ing 10 to 80 µL of sample into the sample boat. The
ensured.
autosampler may be used as long as the accuracy and perfor-
6.10 Humidifier Delivery System, capable of delivering
mance of the method is not degraded.
Type 1 reagent water (7.2) to the combustion tube at a
NOTE 1—Multiple rinsing with clean solvent between sample injections
controlled rate sufficient to provide a pyrohydrolytic environ-
and/or sampling between different sample vials to minimize carryover
ment.
contamination from previous samples is recommended. A solvent flush
from a vial separate from the solvent wash, providing clean, uncontami-
6.11 Ion Chromatograph (IC) , equipped with:
nated solvent may also be used. These features may be used as long as
6.11.1 High Performance inert PEEK-
they do not degrade the performance and accuracy of the method.
(polyetheretherketone) flow path system is required.
6.2 Balance, analytical, with sensitivity to 0.0001 g.
6.11.2 High Pressure eluent pump, capable of delivering
6.3 Boat Inlet System—Thesystemprovidesasamplingport
0.0 to 5 mL/min (without eluent generator; 0.1 to 3 mL/min
for the introduction of liquid and solid samples into the sample
(with eluent generator), in 0.01 mL/min increments. Flow rate
boat and is connected to the inlet of the Pyrohydrolytic
accuracy of <1 % of the set value and precision of <2 % is
Combustion Tube. The system is swept by a humidified inert
required.
carrier gas and shall be capable of allowing the quantitative
6.11.3 ConductivityDetector,capableofanoperatingrange
delivery of the material to be analyzed into the pyrohydrolytic
of 0 to 15 000 µS with a linearity correlation coefficient of
oxidation zone at a controlled and repeatable rate.
0.999 and %RSD <5 % at 800 µS. Detector cell constructed of
6.4 Boat Inlet Cooler (Optional)—Sample volatility and
PEEK and capable of maintaining an operating temperature of
injection volume may require an apparatus capable of cooling 30 to 55°C.
the sample boat prior to sample introduction. Thermoelectric
6.11.4 Injection valve, 2 position electrically actuated with
coolers (peltier) or recirculating refrigerated liquid devices are
wetted component material of PEEK (polyetheretherketone).
strongly recommended. Switching sample boats between each
6.11.5 Anion Separator Column AS11HC (4x250mm) or
analysis may prove effective, provided sample size is not too
equivalent, with sufficient capacity for disparate analyte con-
large.
centrations and constructed of PEEK. Capacity of >290
µEquivalents/column with alkanol quartenary ammonium
6.5 Flow Control—The apparatus must be equipped with
functional groups.
flow controllers capable of maintaining a constant supply and
6.11.6 Guard Column AG11HC (4X50mm) or equivalent,
flow of oxygen and argon gas.
packedwithsamematerialforprotectionoftheanionseparator
6.6 Furnace which can maintain a minimum temperature of
column and constructed of PEEK.
900°C.
6.11.7 Post-Column Chemical Suppression Device, capable
6.7 Gas Adsorption Unit, having an adsorption tube of
of reducing the absolute conductivity of eluent concentrations
either 10 or 20 mL which is automatically filled with a known
ofupto200mMKOH(orNaOH).Deliveryofhydroniumions
volume of absorption solution by a built-in burette or other
for suppression by electrolysis of recycled eluent through a
similardevice.TheGasAdsorptionUnitisinterfacedtotheIon
cation exchange membrane.
Chromatograph and injects an aliquot of the adsorption solu-
tion into the Ion Chromatograph after the sample is combusted
and the by-products of combustion are absorbed. The Gas
Many different companies manufacture automatic ion chromatographs. Consult
Adsorption Unit rinses out the gas lines with Type I reagent
the manufacturer for details in setup and operation. Other systems may be used as
water (7.2) from the pyrohydrolytic combustion tube after the
long as precision is shown to be as good as or better than the precision in the
completion of the sample combustion to ensure all the com- method.
D7359 − 08
6.11.8 Eluent Generator (Optional), an eluent generator 7.13 Toluene, Xylene, Isooctane or Methanol, Reagent
capable of producing eluents of 10 to 100 mM KOH with grade. (Other solvents similar to those occurring in samples to
continuous eluent purification can be employed. be analyzed are also acceptable.) Correction for contaminate
6.11.9 Data Acquisition System, such as an integrator or levels of elements of interest must be corrected for (solvent
computer data handling system capable of integrating the peak blank). Alternatively, using a solvent with non-detectable
areas of ion chromatograph. contamination relative to the sample makes the blank correc-
tion unnecessary.
6.12 Quartz or Ceramic Sample Boats of sufficient size to
hold 10 to 80 µL or mg of sample. 7.14 Volumetric Flasks-Type Class A, at the volume speci-
fied to use in this method to prepare standards, reagents and
7. Reagents and Materials
solutions.
7.1 Purity of Reagents—Reagent grade chemicals shall be
7.15 Stock Standard Solutions of approximately-1000 ug/
used in all tests. Unless otherwise indicated, it is intended that
mL—Prepare a stock standard solution by accurately weighing
allreagentsshallconformtothespecificationoftheCommittee
to within 10 % of the target weights for any or all of the target
on Analytical Reagents of the American Chemical Society,
standard compound(s) listed in 7.15.1, 7.15.2, and 7.15.3 into
where such specifications are available. Other grades may be
a 100 mL class A volumetric flask. Dilute to volume with the
used, provided that the reagent is of sufficiently high purity to
selected solvent described in 7.13. Calculate the actual con-
permit its use without lessening the accuracy of the determi-
centration of the stock standard solution(s) for each element by
nation.
usingtheequationbelowwiththeactualrecordedweightofthe
7.2 Purity of Water—Unless otherwise indicated, references target compound used for each element. This stock standard
to water shall be understood to mean Type 1 conforming to
solution can be further diluted to other desired concentrations.
Specification D1193. Other suitable materials, weights and volumes may be substi-
tuted in preparing stock calibration standards as long as the
7.3 Quartz Wool, (fine grade) or other suitable medium.
performance of the method is not degraded.
7.4 Argon, carrier gas minimum 99.9 % purity.
Target Standard Compound(s)
NOTE 2—Purification scrubbers to ensure the removal of containments
7.15.1 Flurobenzoic Acid, (Fluorine), 0.7375 g target
are recommended such as moisture (molecular sieve) and hydrocarbon
trap filters (activated charcoal or equivalent) are recommended. weight.
7.15.2 2,4,5 Trichlorophenol, (Chlorine), 0.1856 g target
7.5 Oxygen, combustion gas minimum 99.6 % purity.
weight.
7.6 Gas Regulators, two-stage, gas regulators capable of
7.15.3 Dibenzothiophene, (Sulfur), 0.5748 g target weight.
regulating the pressures to 40 to 60 psi must be used for the
carrier and combustion gases.
Calculation Formula
7.7 Calibration Standards, certified calibration standards
Stock Standard Solution ~µg/ml! 5 ~A!~B!~10 !/~C!~K! (1)
from commercial sources or calibration standards prepared in
where:
the laboratory containing the elements of interest at the
A = weight of the target compound actually weighed in
concentrations of interest.
grams, g,
NOTE 3—Other calibration standard sources and diluents may be used
B = % concentration of the elements in the respective target
if precision and accuracy are not degraded.
compounds listed in 7.8, 7.9, and 7.10,
NOTE 4—Calibration standards are typically re-mixed and re-certified
C = final diluted volume, mL, and
on a regular basis depending upon frequency of use and age. Calibration
K = 100 (factor correction for %).
standards can have a useful life of about 6 to 12 months if properly stored
in a cool, dark place.
7.16 Phosphate Stock Solution (1.00 mL = 1.00 mg
NOTE 5—A correction for chemical impurity can be used if deemed
Phosphate)—Weigh to within 10 % 1.433 g of potassium
necessary.
dihydrogen phosphate (KH PO ) in water and dilute to 1 L
2 4
7.8 Dibenzothiophene, FW 184.26, 17.399 % S.
with water in a class A volumetric flask and mix well.
7.9 Flurobenzoic Acid, FW 96.10, 13.56 % F.
7.17 Absorbing Solution—Dilute the Phosphate Stock Solu-
7.10 2,4,5 Trichlorophenol, FW 197.46, 53.87 % Cl.
tion with water in a class A volumetric flask to a final
7.11 Hy
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