ASTM D8150-22

Standard Test Method for Determination of Organic Chloride Content in Crude Oil by Distillation Followed by Detection Using Combustion Ion Chromatography

SIGNIFICANCE AND USE
5.1 Organic chlorides do not occur naturally in crude oil. When present, they result from contamination in some manner, such as disposal of chlorinated solvent used in many dewaxing pipeline or other equipment operations.  
5.1.1 Uncontaminated crude oil will contain no detectable organic chloride, and most refineries can handle very small amounts without deleterious effects.
5.1.1.1 Most trade contracts specify that no organic chloride is present in the crude oil.  
5.1.2 Several pipelines have set specification limits less than 1 μg/g organic chlorides in the whole crude, and less than 5 μg/g in the light naphtha, based on the yield of naphtha being 20 % of the original sample.
5.1.2.1 To ensure less than 1 μg/g organic chloride in the crude oil, the amount measured in the naphtha fraction shall be less than 1/f (where f is the naphtha fraction calculated with Eq 1). For example, a crude oil sample with 1 μg/g of organic chloride but a 10 % yield of naphtha would create a naphtha containing 10 μg/g organic chloride. Further, a crude containing 1 μg/g of organic chloride but a 40 % yield of naphtha would create a naphtha containing 2.5 μg/g organic chloride. Due to the difference in naphtha yields, the impact on refining operations can be significantly different.
5.1.2.2 Since crude oil deposits worldwide exhibit different yields of naphtha, the working range of detection for this method shall cover a broad range, possibly as high as 50 μg/g in a naphtha fraction.  
5.1.3 Organic chloride present in the crude oil (for example, methylene chloride, perchloroethylene, etc.) is usually distilled into the naphtha fraction. Some compounds break down during fractionation and produce hydrochloric acid, which has a corrosive effect. Some compounds survive fractionation and are destroyed during hydro-treating (desulfurization of the naphtha).  
5.2 Other halides can also be used for dewaxing crude oil; in such cases, any organic halides will have similar impact on ...
SCOPE
1.1 This test method covers the determination of organic chloride (above 1 μg/g organically-bound chlorine) in crude oils, using distillation and combustion ion chromatography.  
1.2 This test method involves the distillation of crude oil test specimens to obtain a naphtha fraction prior to chloride determination. The chloride content of the naphtha fraction of the whole crude oil can thereby be obtained. See Section 6 regarding potential interferences.  
1.3 The test procedure covers the determination of organic chloride in the washed naphtha fraction of crude oil by combustion ion chromatography. Other halides can be determined but are not included in the precision statement of the test method.  
1.4 The values stated in SI units are to be regarded as standard. The preferred concentration units are micrograms of chloride per gram of sample.  
1.4.1 Exception—The values given in parentheses are for information only.  
1.5 Warning—Mercury has been designated by many regulatory agencies as a hazardous substance that can cause serious medical issues. Mercury, or its vapor, has been demonstrated to be hazardous to health and corrosive to materials. Use caution when handling mercury and mercury-containing products. See the applicable product Safety Data Sheet (SDS) for additional information. The potential exists that selling mercury or mercury-containing products, or both, is prohibited by local or national law. Users must determine legality of sales in their location.  
1.6 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.  
1.7 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision ...

General Information

• Status: Published
• Publication Date: 30-Sep-2022
• ICS: 75.040 - Crude petroleum
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.03 - Elemental Analysis

Relations

• Refers: ASTM D6708-24 - Standard Practice for Statistical Assessment and Improvement of Expected Agreement Between Two Test Methods that Purport to Measure the Same Property of a Material
• Effective Date: 01-Mar-2024
• Refers: ASTM D6300-24 - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 01-Mar-2024
• Refers: ASTM D4175-23a - Standard Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 15-Dec-2023
• Refers: ASTM D6300-23a - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 01-Dec-2023
• Refers: ASTM D86-23ae1 - Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• Effective Date: 01-Dec-2023
• 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 D86-23a - Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• Effective Date: 01-Dec-2023
• Refers: ASTM D4175-23e1 - Standard Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 01-Jul-2023
• Refers: ASTM D6300-19a - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
• Effective Date: 01-Dec-2019
• Refers: ASTM E969-02(2019) - Standard Specification for Glass Volumetric (Transfer) Pipets
• Effective Date: 01-Jul-2019
• Refers: ASTM D6708-19 - Standard Practice for Statistical Assessment and Improvement of Expected Agreement Between Two Test Methods that Purport to Measure the Same Property of a Material
• Effective Date: 01-May-2019
• Refers: ASTM D6708-18 - Standard Practice for Statistical Assessment and Improvement of Expected Agreement Between Two Test Methods that Purport to Measure the Same Property of a Material
• Effective Date: 01-Apr-2018
• 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 E288-10(2017) - Standard Specification for Laboratory Glass Volumetric Flasks
• Effective Date: 01-Nov-2017

Overview

ASTM D8150-22 is the standard test method for determining the organic chloride content in crude oil by distillation, followed by detection using combustion ion chromatography (CIC). Published by ASTM International, this standard provides a robust method for quantifying organically-bound chloride compounds present in crude oils. Organic chlorides are not naturally occurring in crude oil and, when present, are considered contaminants. Their accurate detection is crucial for both quality control and compliance with industry specifications.

This test method is widely adopted by oil refineries, pipeline operators, and trading entities to assess and control the levels of organic chloride contaminants in crude oil supplies. The procedure involves extracting the naphtha fraction from crude oil through distillation, followed by a meticulous wash-and-analyze protocol using CIC, ensuring high sensitivity and reproducibility.

Key Topics

• Significance of Organic Chloride Detection

  • Organic chlorides are typically introduced into crude oil during equipment cleaning or operational processes using chlorinated solvents.
  • Most trade contracts and pipeline specifications require crude oil to be free from detectable organic chlorides.
  • The presence of organic chlorides can lead to formation of hydrochloric acid during refining, causing corrosion and equipment damage.

• Test Method Scope

  • Determines organically-bound chloride above 1 μg/g in crude oils.
  • Utilizes distillation to isolate the naphtha fraction, followed by combustion ion chromatography for chloride quantification.
  • Offers a wide detection range to accommodate varying naphtha yields from different crude sources.

• Sample Preparation and Analysis

  • Involves detailed protocols for sampling, distillation, and cleanup to minimize contamination and ensure accuracy.
  • Washed naphtha fractions are analyzed to determine the true organically-bound chloride content using sensitive CIC instrumentation.

• Safety Considerations

  • Highlights hazards associated with reagents, high temperatures, and toxic substances (e.g., mercury).
  • Advises strict adherence to health, safety, and environmental regulations.

Applications

• Refinery Operations and Quality Control

  • Ensures delivered crude oil meets rigorous specifications for organic chloride content.
  • Prevents corrosion and fouling in refining equipment, safeguarding operational integrity and minimizing maintenance costs.
  • Supports hydro-treating and desulfurization processes by identifying problematic feedstocks.

• Pipeline and Trading Requirements

  • Verifies compliance with pipeline limits (such as less than 1 μg/g in whole crude).
  • Facilitates custody transfer and contractual agreements by providing a standardized measurement.

• Environmental and Regulatory Compliance

  • Detects and controls organic halide contaminants, contributing to environmental protection efforts.
  • Aligns with international quality and safety standards for the oil and gas industry.

Related Standards

The following ASTM standards are closely related to D8150-22 and support its implementation:

• ASTM D86 - Standard Test Method for Distillation of Petroleum Products and Liquid Fuels
• ASTM D4929 - Standard Test Method for Determination of Organic Chloride Content in Crude Oil
• ASTM D4057 / D4177 - Practices for Manual and Automatic Sampling of Petroleum and Petroleum Products
• ASTM D1193 - Specification for Reagent Water
• ASTM D4052 / D1298 - Test Methods for Density and API Gravity of Liquids

These standards collectively provide comprehensive guidelines for sampling, preparation, analysis, and quality control in petroleum product testing.

---

Keywords: ASTM D8150-22, organic chloride content, crude oil analysis, combustion ion chromatography, oil refinery, naphtha fraction, petroleum testing, corrosion prevention, pipeline specifications, organic halide detection, crude oil quality assurance.

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: D8150 − 22
Standard Test Method for
Determination of Organic Chloride Content in Crude Oil by
Distillation Followed by Detection Using Combustion Ion
Chromatography
This standard is issued under the fixed designation D8150; 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* priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
1.1 This test method covers the determination of organic
1.7 This international standard was developed in accor-
chloride (above 1 µg/g organically-bound chlorine) in crude
dance with internationally recognized principles on standard-
oils, using distillation and combustion ion chromatography.
ization established in the Decision on Principles for the
1.2 This test method involves the distillation of crude oil
Development of International Standards, Guides and Recom-
test specimens to obtain a naphtha fraction prior to chloride
mendations issued by the World Trade Organization Technical
determination. The chloride content of the naphtha fraction of
Barriers to Trade (TBT) Committee.
the whole crude oil can thereby be obtained. See Section 6
regarding potential interferences.
2. Referenced Documents
1.3 The test procedure covers the determination of organic
2.1 ASTM Standards:
chloride in the washed naphtha fraction of crude oil by
D86 Test Method for Distillation of Petroleum Products and
combustion ion chromatography. Other halides can be deter-
Liquid Fuels at Atmospheric Pressure
minedbutarenotincludedintheprecisionstatementofthetest
D1193 Specification for Reagent Water
method.
D1298 Test Method for Density, Relative Density, or API
Gravity of Crude Petroleum and Liquid Petroleum Prod-
1.4 The values stated in SI units are to be regarded as
ucts by Hydrometer Method
standard. The preferred concentration units are micrograms of
D4052 Test Method for Density, Relative Density, and API
chloride per gram of sample.
Gravity of Liquids by Digital Density Meter
1.4.1 Exception—The values given in parentheses are for
D4057 Practice for Manual Sampling of Petroleum and
information only.
Petroleum Products
1.5 Warning—Mercuryhasbeendesignatedbymany regu-
D4175 Terminology Relating to Petroleum Products, Liquid
latory agencies as a hazardous substance that can cause serious
Fuels, and Lubricants
medicalissues.Mercury,oritsvapor,hasbeendemonstratedto
D4177 Practice for Automatic Sampling of Petroleum and
be hazardous to health and corrosive to materials. Use caution
Petroleum Products
when handling mercury and mercury-containing products. See
D4929 Test Method for Determination of Organic Chloride
the applicable product Safety Data Sheet (SDS) for additional
Content in Crude Oil
information. The potential exists that selling mercury or
D6299 Practice for Applying Statistical Quality Assurance
mercury-containing products, or both, is prohibited by local or
and Control Charting Techniques to Evaluate Analytical
national law. Users must determine legality of sales in their
Measurement System Performance
location.
D6300 Practice for Determination of Precision and Bias
1.6 This standard does not purport to address all of the Data for Use in Test Methods for Petroleum Products,
safety concerns, if any, associated with its use. It is the Liquid Fuels, and Lubricants
responsibility of the user of this standard to establish appro- D6708 Practice for StatisticalAssessment and Improvement
of Expected Agreement Between Two Test Methods that
Purport to Measure the Same Property of a Material
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 Oct. 1, 2022. Published November 2022. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 2017. Last previous edition approved in 2017 as D8150 – 17. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D8150-22. 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
D8150 − 22
E288 Specification for Laboratory Glass Volumetric Flasks less than 1/f (where f is the naphtha fraction calculated with Eq
E969 Specification for Glass Volumetric (Transfer) Pipets 1). For example, a crude oil sample with 1 µg/g of organic
chloride but a 10 % yield of naphtha would create a naphtha
3. Terminology
containing 10 µg/g organic chloride. Further, a crude contain-
ing 1 µg/g of organic chloride but a 40 % yield of naphtha
3.1 Definitions:
would create a naphtha containing 2.5 µg/g organic chloride.
3.1.1 For definitions of terms used in this test method, refer
Due to the difference in naphtha yields, the impact on refining
to Terminology D4175.
operations can be significantly different.
4. Summary of Test Method 5.1.2.2 Since crude oil deposits worldwide exhibit different
yields of naphtha, the working range of detection for this
4.1 Distillation—A crude oil distillation is performed to
method shall cover a broad range, possibly as high as 50 µg/g
obtain the naphtha cut at 204 °C (400 °F). The distillation
in a naphtha fraction.
method was adapted from Test Method D86 for the distillation
5.1.3 Organic chloride present in the crude oil (for example,
of petroleum products as well as Test Method D4929 for
methylene chloride, perchloroethylene, etc.) is usually distilled
determination of organic chloride content in crude oil. The
into the naphtha fraction. Some compounds break down during
naphtha cut is washed with caustic, repeatedly when necessary,
fractionation and produce hydrochloric acid, which has a
until all hydrogen sulfide is removed. The naphtha cut, free of
corrosive effect. Some compounds survive fractionation and
hydrogen sulfide, is then washed with water, repeatedly when
are destroyed during hydro-treating (desulfurization of the
necessary, to remove inorganic halides (chlorides).
naphtha).
4.2 Detection Using Combustion Ion Chromatography—A
5.2 Otherhalidescanalsobeusedfordewaxingcrudeoil;in
sampleofknownweightorvolumeisplacedintoasampleboat
such cases, any organic halides will have similar impact on the
and introduced at a controlled rate into a high temperature
refining operations as the organic chlorides.
combustion tube.There, the sample is combusted in an oxygen
rich pyrohydrolytic environment. The gaseous by-products of 5.3 Organic chloride species are potentially damaging to
the combusted sample are trapped in an absorption medium
refinery processes. Hydrochloric acid can be produced in
where the hydrogen halides (HX) formed during combustion
hydro- treating or reforming reactors and the acid accumulates
-
disassociate into their respective ions, X while the sulfur
in condensing regions of the refinery. Unexpected concentra-
2-
oxides (SO ) formed are further oxidized to SO in the
tions of organic chlorides cannot be effectively neutralized and
X 4
presenceofanoxidizingagent.Analiquotofknownvolumeof
damage can result. Organic chlorides are not known to be
theabsorbingsolutionisthenautomaticallyinjectedintoanion
naturally present in crude oils and usually result from cleaning
chromatograph (IC) by means of a sample injection valve. The operationsatproducingsites,pipelines,ortanks.Itisimportant
halide and sulfate anions are separated on the anion separation
for the oil industry to have common methods available for the
column of the IC. The conductivity of the eluent is reduced determination of organic chlorides in crude oil, particularly
with an anion suppression device prior to the ion chromato-
when transfer of custody is involved.
graph’s conductivity detector, where the anions of interest are
measured. Quantification of the chlorine in the original com-
6. Interferences
busted sample is achieved by first calibrating the system with
6.1 Detection Using Combustion Ion Chromatography—
aseriesofstandardscontainingknownamountsofchlorineand
Substances that co-elute with the anions of interest will
then analyzing unknown samples under the same conditions as
interfere. A high concentration of one anion can interfere with
the standards. The combined system of pyrohydrolytic com-
other constituents if their retention times are close enough to
bustion followed by ion chromatographic detection is referred
affect the resolution of their peak.
to as Combustion Ion Chromatography (CIC).
7. Purity of Reagents
5. Significance and Use
7.1 Purity of Reagents—Reagent grade chemicals shall be
5.1 Organic chlorides do not occur naturally in crude oil.
used in all tests. Unless otherwise indicated, it is intended that
When present, they result from contamination in some manner,
all reagents shall conform to the specifications of the Commit-
such as disposal of chlorinated solvent used in many dewaxing
tee onAnalytical Reagents of theAmerican Chemical Society,
pipeline or other equipment operations.
where such specifications are available. Other grades can be
5.1.1 Uncontaminated crude oil will contain no detectable
used, provided it is first ascertained that the reagent is of
organic chloride, and most refineries can handle very small
sufficiently high purity to permit its use without lessening the
amounts without deleterious effects.
accuracy of the determination.
5.1.1.1 Most tradecontractsspecifythatnoorganic chloride
is present in the crude oil.
5.1.2 Severalpipelineshavesetspecificationlimitslessthan
1 µg/g organic chlorides in the whole crude, and less than 5
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington,
µg/g in the light naphtha, based on the yield of naphtha being
DC. For suggestions on the testing of reagents not listed by theAmerican Chemical
20 % of the original sample.
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
5.1.2.1 To ensure less than 1 µg/g organic chloride in the
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
crude oil, the amount measured in the naphtha fraction shall be copeial Convention, Inc. (USPC), Rockville, MD.
D8150 − 22
7.2 Purity of Water—Unless otherwise indicated, references 9.6 Toluene, chloride-free. (Warning—Flammable. Health
to water shall be understood to mean reagent water as defined hazard.)
by Type I of Specification D1193.
10. Sampling
DISTILLATION AND CLEANUP PROCEDURE
10.1 ObtainatestunitinaccordancewithPracticeD4057or
D4177. To preserve volatile components, which are in some
8. Apparatus
samples, do not uncover samples any longer than necessary.
Samples should be analyzed as soon as possible, after taking
8.1 Round-Bottom Boiling Flask, borosilicate, 1 L, single
from bulk supplies, to prevent loss of organic chloride or
short neck with 24/40 outer ground-glass joint.
contamination due to exposure or contact with sample con-
8.2 Tee Adapter, borosilicate, 75° angle side-arm, 24/40
tainer. (Warning—Samples that are collected at temperatures
ground-glass joints.
below room temperature can undergo expansion and rupture
8.3 Thermometer,ASTMthermometer2C(–5 °Cto300 °C)
the container. For such samples, do not fill the container to the
or 2F, (20 °F to 580 °F).
top; leave sufficient air space above the sample to allow room
8.3.1 Other temperature measuring devices, such as thermo-
for expansion.)
couples or resistance thermometers, can be used when the
10.2 Ifthetestunitisnotusedimmediately,thenthoroughly
temperature reading obtained by these devices is determined to
mix in its container prior to taking a test specimen. Some test
produce the same naphtha fraction that is obtained when
units can require heating to ensure sample homogenization.
mercury-in-glass thermometers are used.
(Warning—When heating is required, care should be taken so
8.4 Thermometer Adapter, borosilicate, 24/40 inner ground-
that no organic chloride containing hydrocarbons are lost.)
glass joint.
11. Preparation of Distillation Apparatus
8.5 Liebig Condenser, borosilicate, 300 mm length, 24/40
11.1 Clean all glassware by rinsing successively with tolu-
ground-glass joints.
ene and acetone.After completing the rinse, dry the glassware
8.6 Vacuum Take-Off Adapter,borosilicate,105°anglebend,
using a stream of dry nitrogen gas. Obtain and record the
24/40 ground-glass joints.
masses of the round-bottom flask and receiving cylinder.
Assembletheglassdistillationapparatususingstopcockgrease
8.7 Receiving Cylinder,borosilicate,250 mLcapacity,24/40
to seal all joints and wire clamps to prevent loosening of the
outer ground-glass joint.
joints. Adjust the thermometer position within the adapter tee
8.8 Wire Clamps, for No. 24 ground-glass joints, stainless
suchthatthelowerendofthecapillaryislevelwiththehighest
steel.
point on the bottom of the inner wall of the adapter tee section
8.9 Receiver Flask, for ice bath, 4 L.
that connects to the condenser.
NOTE 1—A diagram illustrating the appropriate positioning of the
8.10 Copper Tubing, for heat exchanger to cool condenser
thermometer can be found in Test Method D86.
water, 6.4 mm outside diameter, 3 m length.
11.2 Form the copper tubing into a coil to fit inside the
8.11 Electric Heating Mantle, Glas-Col Series 0, 1 L size,
receiver flask, leaving room in the center of the flask for the
140 W upper heating element, 380 W lower heating element,
receiving cylinder. With the PVC tubing, connect one end of
or equivalent.
the copper coil to the water source, and connect the other end
8.12 Variable Transformer, 2, for temperature control of
of the coil to the lower fitting of the Liebig condenser cooling
upper and lower heating elements, 120 V, 10 amps.
jacket. Connect the upper condenser fitting to the water drain.
Fillthereceiverflaskwithanice/watermixture,andturnonthe
9. Reagents and Materials
water. Maintain the temperature of the condenser below 10 °C.
9.1 Acetone, chloride-free. (Warning—Extremely
12. Procedure
flammable, can cause flash fires. Health hazard.)
12.1 Add a 500 mLcrude oil test specimen to a tared round
9.2 Caustic Solution, 1 M potassium hydroxide
bottom flask. Obtain and record the mass of the crude oil-filled
(Warning—Can cause severe burns to skin.) prepared in
flask to the nearest 0.1 g. Connect the flask to the distillation
distilled/deionized water.
apparatus. Place the heating mantle around the flask, and
support the heating mantle/flask from the bottom. Connect the
9.3 Deionized Water.
heating mantle to the variacs. Turn on the variacs and start the
9.4 Filter Paper, Whatman No. 41 or equivalent.
distillation. During the distillation, adjust the variac settings to
9.5 Stopcock Grease.
give a distillation rate of approximately 5 mL⁄min. Continue
the distillation until a thermometer reading of 204 °C (400 °F)
isattained.Whenthetemperaturereaches204 °C(400 °F),end
the distillation by first disconnecting and removing the receiv-
The sole source of supply of the stop-cock grease known to the committee at
this time is Dow Corning silicone, available from Dow Corning Corporation,
ing cylinder. After the receiving cylinder has been removed,
Corporate Center, PO Box 994, Midland, MI. If you are aware of alternative
turn off the variacs and remove the heating mantle from the
suppliers, please provide this information to ASTM International Headquarters.
flask. Obtain and record the mass of the receiving cylinder and
Your comments will receive careful consideration at a meeting of the responsible
technical committee, which you may attend. distillate.
D8150 − 22
NOTE 2—Appendix X2 describes a caution regarding crude oil sample NOTE 4—The sample syringe should be rinsed with clean solvent
preparation using water washing prior to distillation. While this method followed by a rinse with the next sample when changing from one vial to
permits water washing of the distilled naphtha, as described in Section another. Follow the manufacturer’s recommendation to minimize carry-
12.2, it does not include neat sample preparation by water washing of the over.
crude oil sample prior to testing. The information provided in Appendix
14.2 Balance, analytical, with sensitivity to 0.0001 g.
X2 should not be interpreted as support for this preparation practice.
14.3 Boat Inlet System, The system provides a sampling
12.1.1 The precision and bias statements were determined
port for the introduction of liquid samples into the sample boat
using mercury-in-glass thermometers only. Therefore, when
and is connected to the inlet of the combustion tube. The
alternativee temperature measuring devices are used, the cut-
system is swept by a humidified inert carrier gas and shall be
off temperature shall be that which will produce a naphtha cut
capable of allowing the quantitative delivery of the material to
similar to what would be yielded when mercury-in-glass
be analyzed into the oxidation zone at a controlled rate.
thermometers are used. Such alternative temperature measur-
ing devices shall not be expected to exhibit the same tempera-
14.4 Boat Inlet Cooler—Sample volatility requires an appa-
ture lag characteristics as mercury-in-glass thermometers.
ratus capable of cooling the sample boat prior to sample
injection into the boat.
12.2 Transfer the naphtha fraction from the receiving cyl-
inder to a separatory funnel. Using the separatory funnel, wash
14.5 Gas Flow Control—The apparatus shall be equipped
the naphtha fraction three times with equal volumes of the
with flow controllers capable of maintaining a constant flow of
caustic solution (1 M KOH). Follow the caustic wash with a
oxygen and argon or helium carrier gas.
water wash, again washing three times with equal volumes.
14.5.1 Gas Regulators, two-stage, gas regulators capable of
The caustic wash removes hydrogen sulfide, while the water
regulating the pressures to 40 psi to 60 psi shall be used for the
wash removes traces of inorganic chlorides either originally
carrier and combustion gases. Follow instrument manufactur-
present in the crude or from impurities in the caustic solution.
er’s recommendations for pressure regulation.
After the washings are complete, filter the naphtha fraction to
14.6 Furnace—An electric furnace which can maintain a
remove residual freestanding water. Store the naphtha fraction
minimum temperature of 900 °C.
in a clean glass bottle. This naphtha fraction can now be
analyzed for organic chlorides by combustion ion chromatog-
14.7 Gas Absorption Unit, having an absorption tube with
raphy.
sufficient capacity to hold a minimum of 5 mL which is
12.3 Measure the density of the crude oil specimen and the automatically filled with a known volume of absorption solu-
naphtha fraction by obtaining the mass of 10.0 mL (using a tion by a built-in burette or other similar device. The gas
10 mL volumetric flask) of each to the nearest 0.1 g. absorption unit is interfaced to the IC and injects an aliquot of
NOTE 3—Alternatively, the density of the crude oil specimen and the
the absorption solution into the IC after the sample is com-
naphtha fraction can be determined using a digital density meter as
busted and the by- products of combustion are absorbed. The
specified in Test Method D4052.
gas absorption unit rinses the absorption tube and the transfer
lines from the combustion tube to the gas absorption unit with
13. Calculation
Type I reagent water ( 9.3) or other appropriate absorption
13.1 Calculatethenaphthafraction, f,usingEq1asfollows:
solution prior to sample combustion and after the absorption
solution is injected into the IC to minimize cross contamina-
M
n
f 5 (1)
tion.
M
c
14.8 Gas-Tight Sampling Syringe, of 10 µL, 25 µL, 50 µL,
where:
100 µL, or 250 µL capacity and capable of accurately deliver-
f = mass fraction of naphtha collected,
ing microliter quantities.
M = mass of naphtha collected, and
n
M = mass of crude oil specimen.
c
14.9 Pyrohydrolytic Combustion Tube, made of quartz and
capable of withstanding temperatures up to 1100 °C. The
13.2 Calculate the density of the naphtha fraction using Eq
combustion tube shall be of ample volume and can include
2 as follows:
quartz wool or other suitable medium to provide sufficient
m
Density, g/mL 5 (2) mixing and surface area to ensure complete combustion of the
v
sample.
where:
14.10 Humidifier Delivery System, capable of delivering
m = mass of sample specimen, g, and
Type 1 reagent water (Section 9.3) to the combustion tube at a
v = volume of sample specimen, mL.
controlled rate sufficient to provide a pyrohydrolytic environ-
ment.
DETECTION USING COMBUSTION ION
CHROMATOGRAPHY
14.11 Ion Chromatograph (IC), (see Note 5) an analytical
system with all required accessories including columns, sup-
14. Apparatus
pressor and detector.
14.1 Autosampler, capable of accurately delivering a known
NOTE 5—Many different companies manufacture automatic ion chro-
volume of sample, typically in the range of 10 µL to 100 µL,
matographs. Consult the specific manufacturer instruction manuals for
into the sample boat. details regarding setup and operation.
D8150 − 22
14.11.1 Injection System, capable of delivering 20 µL to 14.12 Quartz or Ceramic Sample Boats, of sufficient size to
500 µLwithaprecisionbetterthan1 %orasrecommendedfor hold 10 µL to 100 µL. The boat is filled with quartz wool or
this determination by the manufacturer. Larger volumes can be othersuitablematerial(9.4)towickanyremainingdropsofthe
used as long as the performance criteria of the method are not sample from the tip of the syringe needle prior to introduction
degraded. of the sample into the furnace.
14.11.2 Pumping System, capable of delivering mobile
14.13 Volumetric Flasks–Type Class A, in accordance with
phase flows between 0.2 mL⁄min and 2.5 mL/min with a
Specification E288 at the volume required for the preparation
precision better than 2 %, or as recommended for this deter-
of standards, reagents, and solutions.
mination by the manufacturer.
14.14 Volumetric Pipets–Type Class A, in accordance with
14.11.3 Continuous Eluent Generation (optional), to auto-
Specification E969 at the volume required for preparation of
matically prepare and purify the eluent used in the ion
standards, reagents, and solutions.
chromatography. Electrolytic eluent generation and auto-buret
preparation of eluent by means of in-line dilution of a stock
15. Reagents and Materials
solution have been found satisfactory for this method. Other
15.1 Purity of Reagents—Reagent grade or higher purity
continuous eluent generation devices can be used if the
chemicals shall be used for the preparation of all samples,
precision and accuracy of the method are not degraded.
standards, eluent, and regenerator solutions. Unless otherwise
14.11.4 Anion Pre-concentration Column (optional), used
indicated, it is intended that all reagents shall conform to the
for anion pre-concentration and matrix elimination. Pre- con-
specification of the Committee on Analytical Reagents of the
centration enables larger volumes of absorbing solu-
American Chemical Society, where such specifications are
tion (1 mL to 3 mL) to be analyzed without the associated
available. Other grades can be used, provided that the reagent
water dip. Matrix elimination refers to the elimination of any
is of sufficiently high purity to permit its use without lessening
unreacted hydrogen peroxide in the absorbing solution prior to
the accuracy of the determination.
injection onto the guard and anion separator columns and
NOTE 6—Purity of reagents are of particular importance when perform-
potentially interfere with the fluoride peak resolution.
ing trace analysis (samples containing 1 mg/kg or less in analyte
14.11.5 Guard Column, for protection of the analytical
concentration).Asystem reagent blank should provide a chromatographic
column from strongly retained constituents. Improved separa-
area response no greater than 50 % ( ⁄2) of the lowest calibration standard.
tion is obtained with additional theoretical plates.
15.2 Purity of Water
...

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: D8150 − 17 D8150 − 22
Standard Test Method for
Determination of Organic Chloride Content in Crude Oil by
Distillation Followed by Detection Using Combustion Ion
Chromatography
This standard is issued under the fixed designation D8150; 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 Scope*
1.1 This test method covers the determination of organic chloride (above 1 μg/g organically-bound chlorine) in crude oils, using
distillation and combustion ion chromatography.
1.2 This test method involves the distillation of crude oil test specimens to obtain a naphtha fraction prior to chloride
determination. The chloride content of the naphtha fraction of the whole crude oil can thereby be obtained. See Section 56
regarding potential interferences.
1.3 The test procedure covers the determination of organic chloride in the washed naphtha fraction of crude oil by combustion
ion chromatography. Other halides can be determined but are not included in the precision statement of the test method.
1.4 The values stated in SI units are to be regarded as standard. The preferred concentration units are micrograms of chloride per
gram of sample.
1.4.1 Exception—The values given in parentheses are for information only.
1.5 Warning—Mercury has been designated by many regulatory agencies as a hazardous materialsubstance that can cause central
nervous system, kidney and liver damage. serious medical issues. Mercury, or its vapor, may has been demonstrated to be
hazardous to health and corrosive to materials. Caution should be taken Use caution when handling mercury and mercury
containing mercury-containing products. See the applicable product Material Safety Data Sheet (MSDS) for details and EPA’s
website—http://www.epa.gov/mercury/faq.htm—for additional information. Users should be aware (SDS) for additional informa-
tion. The potential exists that selling mercury and/or mercury containing products into your state or country may be prohibited by
law.or mercury-containing products, or both, is prohibited by local or national law. Users must determine legality of sales in their
location.
1.6 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.
1.7 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.
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 Oct. 1, 2017Oct. 1, 2022. Published November 2017November 2022. Originally approved in 2017. Last previous edition approved in 2017 as
D8150 – 17. DOI: 10.1520/D8150-17.10.1520/D8150-22.
*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
D8150 − 22
2. Referenced Documents
2.1 ASTM Standards:
D86 Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
D1193 Specification for Reagent Water
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
D4175 Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D4929 Test Method for Determination of Organic Chloride Content in Crude Oil
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
D6300 Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products, Liquid Fuels, and
Lubricants
D6708 Practice for Statistical Assessment and Improvement of Expected Agreement Between Two Test Methods that Purport
to Measure the Same Property of a Material
E288 Specification for Laboratory Glass Volumetric Flasks
E969 Specification for Glass Volumetric (Transfer) Pipets
3. Terminology
3.1 Definitions:
3.1.1 For definitions of terms used in this test method, refer to Terminology D4175.
4. Summary of Test Method
4.1 Distillation—A crude oil distillation is performed to obtain the naphtha cut at 204 °C (400 °F). The distillation method was
adapted from Test Method D86 for the distillation of petroleum products as well as Test Method D4929 for determination of
organic chloride content in crude oil. The naphtha cut is washed with caustic, repeatedly when necessary, until all hydrogen sulfide
is removed. The naphtha cut, free of hydrogen sulfide, is then washed with water, repeatedly when necessary, to remove inorganic
halides (chlorides).
4.2 Detection Using Combustion Ion Chromatography—A sample of known weight or volume is placed into a sample boat and
introduced at a controlled rate into a high temperature combustion tube. There, the sample is combusted in an oxygen rich
pyrohydrolytic environment. The gaseous by-products of the combusted sample are trapped in an absorption medium where the
-
hydrogen halides (HX) formed during combustion disassociate into their respective ions, X while the sulfur oxides (SO ) formed
X
2-
are further oxidized to SO in the presence of an oxidizing agent. An aliquot of known volume of the absorbing solution is then
automatically injected into an ion chromatograph (IC) by means of a sample injection valve. The halide and sulfate anions are
separated on the anion separation column of the IC. The conductivity of the eluent is reduced with an anion suppression device
prior to the ion chromatograph’s conductivity detector, where the anions of interest are measured. Quantification of the chlorine
in the original combusted sample is achieved by first calibrating the system with a series of standards containing known amounts
of chlorine and then analyzing unknown samples under the same conditions as the standards. The combined system of
pyrohydrolytic combustion followed by ion chromatographic detection is referred to as Combustion Ion Chromatography (CIC).
5. Significance and Use
5.1 Organic chlorides do not occur naturally in crude oil. When present, they result from contamination in some manner, such as
disposal of chlorinated solvent used in many dewaxing pipeline or other equipment operations.
5.1.1 Uncontaminated crude oil will contain no detectable organic chloride, and most refineries can handle very small amounts
without deleterious effects.
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.
D8150 − 22
5.1.1.1 Most trade contracts specify that no organic chloride is present in the crude oil.
5.1.2 Several pipelines have set specification limits less than 1 μg/g organic chlorides in the whole crude, and less than 5 μg/g in
the light naphtha, based on the yield of naphtha being 20 % of the original sample.
5.1.2.1 To ensure less than 1 μg/g organic chloride in the crude oil, the amount measured in the naphtha fraction shall be less than
1/f (where f is the naphtha fraction calculated with Eq 1). For example, a crude oil sample with 1 μg/g of organic chloride but a
10 % yield of naphtha would create a naphtha containing 10 μg/g organic chloride. Further, a crude containing 1 μg/g of organic
chloride but a 40 % yield of naphtha would create a naphtha containing 2.5 μg/g organic chloride. Due to the difference in naphtha
yields, the impact on refining operations can be significantly different.
5.1.2.2 Since crude oil deposits worldwide exhibit different yields of naphtha, the working range of detection for this method shall
cover a broad range, possibly as high as 50 μg/g in a naphtha fraction.
5.1.3 Organic chloride present in the crude oil (for example, methylene chloride, perchloroethylene, etc.) is usually distilled into
the naphtha fraction. Some compounds break down during fractionation and produce hydrochloric acid, which has a corrosive
effect. Some compounds survive fractionation and are destroyed during hydro-treating (desulfurization of the naphtha).
5.2 Other halides can also be used for dewaxing crude oil; in such cases, any organic halides will have similar impact on the
refining operations as the organic chlorides.
5.3 Organic chloride species are potentially damaging to refinery processes. Hydrochloric acid can be produced in hydro- treating
or reforming reactors and the acid accumulates in condensing regions of the refinery. Unexpected concentrations of organic
chlorides cannot be effectively neutralized and damage can result. Organic chlorides are not known to be naturally present in crude
oils and usually result from cleaning operations at producing sites, pipelines, or tanks. It is important for the oil industry to have
common methods available for the determination of organic chlorides in crude oil, particularly when transfer of custody is
involved.
6. Interferences
6.1 Detection Using Combustion Ion Chromatography—Substances that co-elute with the anions of interest will interfere. A high
concentration of one anion can interfere with other constituents if their retention times are close enough to affect the resolution
of their peak.
7. Purity of Reagents
7.1 Purity of Reagents—Reagent grade chemicals shall be used in all 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 can 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 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water as defined by Type
I of Specification D1193.
DISTILLATION AND CLEANUP PROCEDURE
8. Apparatus
8.1 Round-Bottom Boiling Flask, borosilicate, 1 L, single short neck with 24/40 outer ground-glass joint.
8.2 Tee Adapter, borosilicate, 75° angle side-arm, 24/40 ground-glass joints.
Reagent Chemicals, American Chemical Society Specifications,ACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference
Materials, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar 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.
D8150 − 22
8.3 Thermometer, ASTM thermometer 2C (–5 °C to 300 °C) or 2F, (20 °F to 580 °F).
8.3.1 Other temperature measuring devices, such as thermocouples or resistance thermometers, can be used when the temperature
reading obtained by these devices is determined to produce the same naphtha fraction that is obtained when mercury-in-glass
thermometers are used.
8.4 Thermometer Adapter, borosilicate, 24/40 inner ground-glass joint.
8.5 Liebig Condenser, borosilicate, 300 mm length, 24/40 ground-glass joints.
8.6 Vacuum Take-Off Adapter, borosilicate, 105° angle bend, 24/40 ground-glass joints.
8.7 Receiving Cylinder, borosilicate, 250 mL capacity, 24/40 outer ground-glass joint.
8.8 Wire Clamps, for No. 24 ground-glass joints, stainless steel.
8.9 Receiver Flask, for ice bath, 4 L.
8.10 Copper Tubing, for heat exchanger to cool condenser water, 6.4 mm outside diameter, 3 m length.
8.11 Electric Heating Mantle, Glas-Col Series 0, 1 L size, 140 W upper heating element, 380 W lower heating element, or
equivalent.
8.12 Variable Transformer, 2, for temperature control of upper and lower heating elements, 120 V, 10 amps.
9. Reagents and Materials
9.1 Acetone, chloride-free. (Warning—Extremely flammable, can cause flash fires. Health hazard.)
9.2 Caustic Solution, 1 M potassium hydroxide (Warning—Can cause severe burns to skin.) prepared in distilled/deionized water.
9.3 Deionized Water.
9.4 Filter Paper, Whatman No. 41 or equivalent.
9.5 Stopcock Grease.
9.6 Toluene, chloride-free. (Warning—Flammable. Health hazard.)
10. Sampling
10.1 Obtain a test unit in accordance with Practice D4057 or D4177. To preserve volatile components, which are in some samples,
do not uncover samples any longer than necessary. Samples should be analyzed as soon as possible, after taking from bulk supplies,
to prevent loss of organic chloride 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.)
10.2 If the test unit is not used immediately, then thoroughly mix in its container prior to taking a test specimen. Some test units
The sole source of supply of the stop-cock grease known to the committee at this time is Dow Corning silicone, available from Dow Corning Corporation, Corporate
Center, PO Box 994, Midland, MI. If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive
careful consideration at a meeting of the responsible technical committee, which you may attend.
D8150 − 22
can require heating to ensure sample homogenization. (Warning—When heating is required, care should be taken so that no
organic chloride containing hydrocarbons are lost.)
11. Preparation of Distillation Apparatus
11.1 Clean all glassware by rinsing successively with toluene and acetone. After completing the rinse, dry the glassware using a
stream of dry nitrogen gas. Obtain and record the masses of the round-bottom flask and receiving cylinder. Assemble the glass
distillation apparatus using stopcock grease to seal all joints and wire clamps to prevent loosening of the joints. Adjust the
thermometer position within the adapter tee such that the lower end of the capillary is level with the highest point on the bottom
of the inner wall of the adapter tee section that connects to the condenser.
NOTE 1—A diagram illustrating the appropriate positioning of the thermometer can be found in Test Method D86.
11.2 Form the copper tubing into a coil to fit inside the receiver flask, leaving room in the center of the flask for the receiving
cylinder. With the PVC tubing, connect one end of the copper coil to the water source, and connect the other end of the coil to
the lower fitting of the Liebig condenser cooling jacket. Connect the upper condenser fitting to the water drain. Fill the receiver
flask with an ice/water mixture, and turn on the water. Maintain the temperature of the condenser below 10 °C.
12. Procedure
12.1 Add a 500 mL crude oil test specimen to a tared round bottom flask. Obtain and record the mass of the crude oil-filled flask
to the nearest 0.1 g. Connect the flask to the distillation apparatus. Place the heating mantle around the flask, and support the
heating mantle/flask from the bottom. Connect the heating mantle to the variacs. Turn on the variacs and start the distillation.
During the distillation, adjust the variac settings to give a distillation rate of approximately 5 mL ⁄min. Continue the distillation
until a thermometer reading of 204 °C (400 °F) is attained. When the temperature reaches 204 °C (400 °F), end the distillation by
first disconnecting and removing the receiving cylinder. After the receiving cylinder has been removed, turn off the variacs and
remove the heating mantle from the flask. Obtain and record the mass of the receiving cylinder and distillate.
NOTE 2—Appendix X2 describes a caution regarding crude oil sample preparation using water washing prior to distillation. While this method permits
water washing of the distilled naphtha, as described in Section 11.212.2, it does not include neat sample preparation by water washing of the crude oil
sample prior to testing. The information provided in Appendix X2 should not be interpreted as support for this preparation practice.
12.1.1 The precision and bias statements were determined using mercury-in-glass thermometers only. Therefore, when alternativee
temperature measuring devices are used, the cut-off temperature shall be that which will produce a naphtha cut similar to what
would be yielded when mercury-in-glass thermometers are used. Such alternative temperature measuring devices shall not be
expected to exhibit the same temperature lag characteristics as mercury-in-glass thermometers.
12.2 Transfer the naphtha fraction from the receiving cylinder to a separatory funnel. Using the separatory funnel, wash the
naphtha fraction three times with equal volumes of the caustic solution (1 M KOH). Follow the caustic wash with a water wash,
again washing three times with equal volumes. The caustic wash removes hydrogen sulfide, while the water wash removes traces
of inorganic chlorides either originally present in the crude or from impurities in the caustic solution. After the washings are
complete, filter the naphtha fraction to remove residual freestanding water. Store the naphtha fraction in a clean glass bottle. This
naphtha fraction can now be analyzed for organic chlorides by combustion ion chromatography.
12.3 Measure the density of the crude oil specimen and the naphtha fraction by obtaining the mass of 10.0 mL (using a 10 mL
volumetric flask) of each to the nearest 0.1 g.
NOTE 3—Alternatively, the density of the crude oil specimen and the naphtha fraction can be determined using a digital density meter as specified in Test
Method D4052.
13. Calculation
13.1 Calculate the naphtha fraction, f, using Eq 1 as follows:
M
n
f 5 (1)
M
c
D8150 − 22
where:
f = mass fraction of naphtha collected,
M = mass of naphtha collected, and
n
M = mass of crude oil specimen.
c
13.2 Calculate the density of the naphtha fraction using Eq 2 as follows:
m
Density, g/mL 5 (2)
v
where:
m = mass of sample specimen, g, and
v = volume of sample specimen, mL.
DETECTION USING COMBUSTION ION CHROMATOGRAPHY
14. Apparatus
14.1 Autosampler, capable of accurately delivering a known volume of sample, typically in the range of 10 μL to 100 μL, into the
sample boat.
NOTE 4—The sample syringe should be rinsed with clean solvent followed by a rinse with the next sample when changing from one vial to another. Follow
the manufacturer’s recommendation to minimize carryover.
14.2 Balance, analytical, with sensitivity to 0.0001 g.
14.3 Boat Inlet System, The system provides a sampling port for the introduction of liquid samples into the sample boat and is
connected to the inlet of the combustion tube. The system is swept by a humidified inert carrier gas and shall be capable of allowing
the quantitative delivery of the material to be analyzed into the oxidation zone at a controlled rate.
14.4 Boat Inlet Cooler—Sample volatility requires an apparatus capable of cooling the sample boat prior to sample injection into
the boat.
14.5 Gas Flow Control—The apparatus shall be equipped with flow controllers capable of maintaining a constant flow of oxygen
and argon or helium carrier gas.
14.5.1 Gas Regulators, two-stage, gas regulators capable of regulating the pressures to 40 psi to 60 psi shall be used for the carrier
and combustion gases. Follow instrument manufacturer’s recommendations for pressure regulation.
14.6 Furnace—An electric furnace which can maintain a minimum temperature of 900 °C.
14.7 Gas Absorption Unit, having an absorption tube with sufficient capacity to hold a minimum of 5 mL which is automatically
filled with a known volume of absorption solution by a built-in burette or other similar device. The gas absorption unit is interfaced
to the IC and injects an aliquot of the absorption solution into the IC after the sample is combusted and the by- products of
combustion are absorbed. The gas absorption unit rinses the absorption tube and the transfer lines from the combustion tube to the
gas absorption unit with Type I reagent water ( 8.39.3) or other appropriate absorption solution prior to sample combustion and
after the absorption solution is injected into the IC to minimize cross contamination.
14.8 Gas-Tight Sampling Syringe, of 10 μL, 25 μL, 50 μL, 100 μL, or 250 μL capacity and capable of accurately delivering
microliter quantities.
14.9 Pyrohydrolytic Combustion Tube, made of quartz and capable of withstanding temperatures up to 1100 °C. The combustion
tube shall be of ample volume and can include quartz wool or other suitable medium to provide sufficient mixing and surface area
to ensure complete combustion of the sample.
D8150 − 22
14.10 Humidifier Delivery System, capable of delivering Type 1 reagent water (Section 8.39.3) to the combustion tube at a
controlled rate sufficient to provide a pyrohydrolytic environment.
14.11 Ion Chromatograph (IC), (see Note 5) an analytical system with all required accessories including columns, suppressor and
detector.
NOTE 5—Many different companies manufacture automatic ion chromatographs. Consult the specific manufacturer instruction manuals for details
regarding setup and operation.
14.11.1 Injection System, capable of delivering 20 μL to 500 μL with a precision better than 1 % or as recommended for this
determination by the manufacturer. Larger volumes can be used as long as the performance criteria of the method are not degraded.
14.11.2 Pumping System, capable of delivering mobile phase flows between 0.2 mL ⁄min and 2.5 mL/min with a precision better
than 2 %, or as recommended for this determination by the manufacturer.
14.11.3 Continuous Eluent Generation (optional), to automatically prepare and purify the eluent used in the ion chromatography.
Electrolytic eluent generation and auto-buret preparation of eluent by means of in-line dilution of a stock solution have been found
satisfactory for this method. Other continuous eluent generation devices can be used if the precision and accuracy of the method
are not degraded.
14.11.4 Anion Pre-concentration Column (optional), used for anion pre-concentration and matrix elimination. Pre- concentration
enables larger volumes of absorbing solution (1 mL to 3 mL) to be analyzed without the associated water dip. Matrix elimination
refers to the elimination of any unreacted hydrogen peroxide in the absorbing solution prior to injection onto the guard and anion
separator columns and potentially interfere with the fluoride peak resolution.
14.11.5 Guard Column, for protection of the analytical column from strongly retained constituents. Improved separation is
obtained with additional theoretical plates.
14.11.6 Anion Separator Column, capable of producing satisfactory baseline separation of the anion peak of interest as shown in
Fig. 1.
14.11.7 Anion Suppressor Device, reduces the background conductivity of the eluent after separation by the anion separator
column. Both chemical and continuous electrolytic suppressors have been found satisfactory for this method. Other anion
suppressor devices can be used as long as the precision and accuracy of the method are not degraded.
14.11.8 Conductivity Detector, temperature controlled to 0.01 °C, capable of at least 0 μS ⁄cm to 15 000 μS ⁄cm on a linear scale.
14.11.9 Data Acquisition System, an integrator or computer data handling system capable of integrating the peak areas of the ion
chromatograph.
FIG. 1 Anion Peak of Interest (Chloride)
D8150 − 22
14.12 Quartz or Ceramic Sample Boats, of sufficient size to hold 10 μL to 100 μL. The boat is filled with quartz wool or other
suitable material (8.49.4) to wick any remaining drops of the sample from the tip of the syringe needle prior to introduction of the
sample into the furnace.
14.13 Volumetric Flasks–Type Class A, in accordance with Specification E288 at the volume required for the preparation of
standards, reagents, and solutions.
14.14 Volumetric Pipets–Type Class A, in accordance w
...