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 − 17

Standard Test Method for

Determination of Organic Chloride Content in Crude Oil by
Distillation Followed by Detection Using Combustion Ion
Chromatography1
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-

1.1 This test method covers the determination of organic mine the applicability of regulatory limitations prior to use.
chloride (above 1 µg/g organically-bound chlorine) in crude 1.7 This international standard was developed in accor-
oils, using distillation and combustion ion chromatography. dance with internationally recognized principles on standard-
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 5
regarding potential interferences. 2. Referenced Documents
1.3 The test procedure covers the determination of organic 2.1 ASTM Standards:2
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
mined but are not included in the precision statement of the test D1193 Specification for Reagent Water
method. D1298 Test Method for Density, Relative Density, or API
1.4 The values stated in SI units are to be regarded as Gravity of Crude Petroleum and Liquid Petroleum Prod-
standard. The preferred concentration units are micrograms of ucts by Hydrometer Method
chloride per gram of sample. D4052 Test Method for Density, Relative Density, and API
1.4.1 Exception—The values given in parentheses are for Gravity of Liquids by Digital Density Meter
information only. D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
1.5 Warning—Mercury has been designated by many regu-
D4177 Practice for Automatic Sampling of Petroleum and
latory agencies as a hazardous material that can cause central
Petroleum Products
nervous system, kidney and liver damage. Mercury, or its
D4929 Test Method for Determination of Organic Chloride
vapor, may be hazardous to health and corrosive to materials.
Content in Crude Oil
Caution should be taken when handling mercury and mercury
D6299 Practice for Applying Statistical Quality Assurance
containing products. See the applicable product Material
and Control Charting Techniques to Evaluate Analytical
Safety Data Sheet (MSDS) for details and EPA’s website—
Measurement System Performance
http://www.epa.gov/mercury/faq.htm—for additional informa-
D6300 Practice for Determination of Precision and Bias
tion. Users should be aware that selling mercury and/or
Data for Use in Test Methods for Petroleum Products and
mercury containing products into your state or country may be
Lubricants
prohibited by law.
D6708 Practice for Statistical Assessment and Improvement
1.6 This standard does not purport to address all of the of Expected Agreement Between Two Test Methods that
safety concerns, if any, associated with its use. It is the Purport to Measure the Same Property of a Material
responsibility of the user of this standard to establish appro- E288 Specification for Laboratory Glass Volumetric Flasks
E969 Specification for Glass Volumetric (Transfer) Pipets

1
This test method is under the jurisdiction of ASTM Committee D02 on
2
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Subcommittee D02.03 on Elemental Analysis. contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Current edition approved Oct. 1, 2017. Published November 2017. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D8150-17. the ASTM website.

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 D8150 − 17
3. Summary of Test Method 4.1.2.2 Since crude oil deposits worldwide exhibit different
3.1 Distillation—A crude oil distillation is performed to yields of naphtha, the working range of detection for this
obtain the naphtha cut at 204 °C (400 °F). The distillation method shall cover a broad range, possibly as high as 50 µg/g
method was adapted from Test Method D86 for the distillation in a naphtha fraction.
of petroleum products as well as Test Method D4929 for 4.1.3 Organic chloride present in the crude oil (for example,
determination of organic chloride content in crude oil. The methylene chloride, perchloroethylene, etc.) is usually distilled
naphtha cut is washed with caustic, repeatedly when necessary, into the naphtha fraction. Some compounds break down during
until all hydrogen sulfide is removed. The naphtha cut, free of fractionation and produce hydrochloric acid, which has a
hydrogen sulfide, is then washed with water, repeatedly when corrosive effect. Some compounds survive fractionation and
necessary, to remove inorganic halides (chlorides). are destroyed during hydro-treating (desulfurization of the
naphtha).
3.2 Detection Using Combustion Ion Chromatography—A
sample of known weight or volume is placed into a sample boat 4.2 Other halides can also be used for dewaxing crude oil; in
and introduced at a controlled rate into a high temperature such cases, any organic halides will have similar impact on the
combustion tube. There, the sample is combusted in an oxygen refining operations as the organic chlorides.
rich pyrohydrolytic environment. The gaseous by-products of 4.3 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-
oxides (SOX) formed are further oxidized to SO42- in the tions of organic chlorides cannot be effectively neutralized and
presence of an oxidizing agent. An aliquot of known volume of damage can result. Organic chlorides are not known to be
the absorbing solution is then automatically injected into an ion naturally present in crude oils and usually result from cleaning
chromatograph (IC) by means of a sample injection valve. The operations at producing sites, pipelines, or tanks. It is important
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- 5. Interferences
busted sample is achieved by first calibrating the system with 5.1 Detection Using Combustion Ion Chromatography—
a series of standards containing known amounts of chlorine and 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).
6. Purity of Reagents
4. Significance and Use
6.1 Purity of Reagents—Reagent grade chemicals shall be
4.1 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 on Analytical Reagents of the American Chemical Society,
pipeline or other equipment operations. where such specifications are available.3 Other grades can be
4.1.1 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.
4.1.1.1 Most trade contracts specify that no organic chloride
6.2 Purity of Water—Unless otherwise indicated, references
is present in the crude oil.
to water shall be understood to mean reagent water as defined
4.1.2 Several pipelines have set specification limits less than
by Type I of Specification D1193.
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 DISTILLATION AND CLEANUP PROCEDURE
20 % of the original sample.
4.1.2.1 To ensure less than 1 µg/g organic chloride in the 7. Apparatus
crude oil, the amount measured in the naphtha fraction shall be 7.1 Round-Bottom Boiling Flask, borosilicate, 1 L, single
less than 1/f (where f is the naphtha fraction calculated with Eq short neck with 24/40 outer ground-glass joint.
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 contain- 3
Reagent Chemicals, American Chemical Society Specifications, American
ing 1 µg/g of organic chloride but a 40 % yield of naphtha Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
would create a naphtha containing 2.5 µg/g organic chloride.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Due to the difference in naphtha yields, the impact on refining and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
operations can be significantly different. MD.

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 D8150 − 17
7.2 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
7.3 Thermometer, ASTM thermometer 2C (–5 °C to 300 °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
7.3.1 Other temperature measuring devices, such as thermo- for expansion.)
couples or resistance thermometers, can be used when the 9.2 If the test unit is not used immediately, then thoroughly
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
7.4 Thermometer Adapter, borosilicate, 24/40 inner ground- that no organic chloride containing hydrocarbons are lost.)
glass joint.
10. Preparation of Distillation Apparatus
7.5 Liebig Condenser, borosilicate, 300 mm length, 24/40
ground-glass joints. 10.1 Clean all glassware by rinsing successively with tolu-
7.6 Vacuum Take-Off Adapter, borosilicate, 105° angle bend, ene and acetone. After completing the rinse, dry the glassware
24/40 ground-glass joints. using a stream of dry nitrogen gas. Obtain and record the
masses of the round-bottom flask and receiving cylinder.
7.7 Receiving Cylinder, borosilicate, 250 mL capacity, 24/40 Assemble the glass distillation apparatus using stopcock grease
outer ground-glass joint. to seal all joints and wire clamps to prevent loosening of the
7.8 Wire Clamps, for No. 24 ground-glass joints, stainless joints. Adjust the thermometer position within the adapter tee
steel. 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
7.9 Receiver Flask, for ice bath, 4 L.
that connects to the condenser.
7.10 Copper Tubing, for heat exchanger to cool condenser NOTE 1—A diagram illustrating the appropriate positioning of the
water, 6.4 mm outside diameter, 3 m length. thermometer can be found in Test Method D86.
7.11 Electric Heating Mantle, Glas-Col Series 0, 1 L size, 10.2 Form the copper tubing into a coil to fit inside the
140 W upper heating element, 380 W lower heating element, receiver flask, leaving room in the center of the flask for the
or equivalent. receiving cylinder. With the PVC tubing, connect one end of
7.12 Variable Transformer, 2, for temperature control of the copper coil to the water source, and connect the other end
upper and lower heating elements, 120 V, 10 amps. of the coil to the lower fitting of the Liebig condenser cooling
jacket. Connect the upper condenser fitting to the water drain.
8. Reagents and Materials Fill the receiver flask with an ice/water mixture, and turn on the
8.1 Acetone, chloride-free. (Warning—Extremely water. Maintain the temperature of the condenser below 10 °C.
flammable, can cause flash fires. Health hazard.)
11. Procedure
8.2 Caustic Solution, 1 M potassium hydroxide
(Warning—Can cause severe burns to skin.) prepared in 11.1 Add a 500 mL crude oil test specimen to a tared round
distilled/deionized water. 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
8.3 Deionized Water.
apparatus. Place the heating mantle around the flask, and
8.4 Filter Paper, Whatman No. 41 or equivalent. support the heating mantle/flask from the bottom. Connect the
8.5 Stopcock Grease.4 heating mantle to the variacs. Turn on the variacs and start the
distillation. During the distillation, adjust the variac settings to
8.6 Toluene, chloride-free. (Warning—Flammable. Health
give a distillation rate of approximately 5 mL ⁄min. Continue
hazard.)
the distillation until a thermometer reading of 204 °C (400 °F)
9. Sampling is attained. When the temperature reaches 204 °C (400 °F), end
the distillation by first disconnecting and removing the receiv-
9.1 Obtain a test unit in accordance with Practice D4057 or ing cylinder. After the receiving cylinder has been removed,
D4177. To preserve volatile components, which are in some turn off the variacs and remove the heating mantle from the
samples, do not uncover samples any longer than necessary. flask. Obtain and record the mass of the receiving cylinder and
Samples should be analyzed as soon as possible, after taking distillate.
from bulk supplies, to prevent loss of organic chloride or
contamination due to exposure or contact with sample con- 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
4
The sole source of supply of the stop-cock grease known to the committee at 11.2, it does not include neat sample preparation by water washing of the
this time is Dow Corning silicone, available from Dow Corning Corporation, crude oil sample prior to testing. The information provided in Appendix
Corporate Center, PO Box 994, Midland, MI. If you are aware of alternative X2 should not be interpreted as support for this preparation practice.
suppliers, please provide this information to ASTM International Headquarters.
Your comments will receive careful consideration at a meeting of the responsible 11.1.1 The precision and bias statements were determined
technical committee,1 which you may attend. using mercury-in-glass thermometers only. Therefore, when

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 D8150 − 17
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-
13.4 Boat Inlet Cooler—Sample volatility requires an appa-
ing devices shall not be expected to exhibit the same tempera-
ratus capable of cooling the sample boat prior to sample
ture lag characteristics as mercury-in-glass thermometers.
injection into the boat.
11.2 Transfer the naphtha fraction from the receiving cylin-
der to a separatory funnel. Using the separatory funnel, wash 13.5 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. 13.5.1 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 13.6 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- 13.7 Gas Absorption Unit, having an absorption tube with
raphy. sufficient capacity to hold a minimum of 5 mL which is
automatically filled with a known volume of absorption solu-
11.3 Measure the density of the crude oil specimen and the
tion by a built-in burette or other similar device. The gas
naphtha fraction by obtaining the mass of 10.0 mL (using a
absorption unit is interfaced to the IC and injects an aliquot of
10 mL volumetric flask) of each to the nearest 0.1 g.
the absorption solution into the IC after the sample is com-
NOTE 3—Alternatively, the density of the crude oil specimen and the
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
12. Calculation
Type I reagent water ( 8.3) or other appropriate absorption
12.1 Calculate the naphtha fraction, f, using Eq 1 as follows: solution prior to sample combustion and after the absorption
Mn solution is injected into the IC to minimize cross contamina-
f5 (1) tion.
Mc

where: 13.8 Gas-Tight Sampling Syringe, of 10 µL, 25 µL, 50 µL,

f = mass fraction of naphtha collected, 100 µL, or 250 µL capacity and capable of accurately deliver-
Mn = mass of naphtha collected, and ing microliter quantities.
Mc = mass of crude oil specimen. 13.9 Pyrohydrolytic Combustion Tube, made of quartz and
12.2 Calculate the density of the naphtha fraction using Eq capable of withstanding temperatures up to 1100 °C. The
2 as follows: combustion tube shall be of ample volume and can include
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:
13.10 Humidifier Delivery System, capable of delivering
m = mass of sample specimen, g, and Type 1 reagent water (Section 8.3) to the combustion tube at a
v = volume of sample specimen, mL.
controlled rate sufficient to provide a pyrohydrolytic environ-
DETECTION USING COMBUSTION ION ment.
CHROMATOGRAPHY 13.11 Ion Chromatograph (IC), (see Note 5) an analytical
system with all required accessories including columns, sup-
13. Apparatus
pressor and detector.
13.1 Autosampler, capable of accurately delivering a known
volume of sample, typically in the range of 10 µL to 100 µL, NOTE 5—Many different companies manufacture automatic ion chro-
matographs. Consult the specific manufacturer instruction manuals for
into the sample boat. details regarding setup and operation.
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 13.11.1 Injection System, capable of delivering 20 µL to
another. Follow the manufacturer’s recommendation to minimize carry- 500 µL with a precision better than 1 % or as recommended for
over.
this determination by the manufacturer. Larger volumes can be
13.2 Balance, analytical, with sensitivity to 0.0001 g. used as long as the performance criteria of the method are not
13.3 Boat Inlet System, The system provides a sampling degraded.
port for the introduction of liquid samples into the sample boat 13.11.2 Pumping System, capable of delivering mobile
and is connected to the inlet of the combustion tube. The phase flows between 0.2 mL ⁄min and 2.5 mL/min with a

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 D8150 − 17
precision better than 2 %, or as recommended for this deter- 13.14 Volumetric Pipets–Type Class A, in accordance with
mination by the manufacturer. Specification E969 at the volume required for preparation of
13.11.3 Continuous Eluent Generation (optional), to auto- standards, reagents, and solutions.
matically prepare and purify the eluent used in the ion
chromatography. Electrolytic eluent generation and auto-buret 14. Reagents and Materials
preparation of eluent by means of in-line dilution of a stock 14.1 Purity of Reagents—Reagent grade or higher purity
solution have been found satisfactory for this method. Other chemicals shall be used for the preparation of all samples,
continuous eluent generation devices can be used if the standards, eluent, and regenerator solutions. Unless otherwise
precision and accuracy of the method are not degraded. indicated, it is intended that all reagents shall conform to the
13.11.4 Anion Pre-concentration Column (optional), used specification of the Committee on Analytical Reagents of the
for anion pre-concentration and matrix elimination. Pre- con- American Chemical Society, where such specifications are
centration enables larger volumes of absorbing solu- available.3 Other grades can be used, provided that the reagent
tion (1 mL to 3 mL) to be analyzed without the associated is of sufficiently high purity to permit its use without lessening
water dip. Matrix elimination refers to the elimination of any the accuracy of the determination.
unreacted hydrogen peroxide in the absorbing solution prior to NOTE 6—Purity of reagents are of particular importance when perform-
injection onto the guard and anion separator columns and ing trace analysis (samples containing 1 mg/kg or less in analyte
concentration). A system reagent blank should provide a chromatographic
potentially interfere with the fluoride peak resolution.
area response no greater than 50 % (1⁄2) of the lowest calibration standard.
13.11.5 Guard Column, for protection of the analytical
column from strongly retained constituents. Improved separa- 14.2 Purity of Water—Unless otherwise indicated, refer-
tion is obtained with additional theoretical plates. ences to water shall be understood to mean Type 1 having
13.11.6 Anion Separator Column, capable of producing 18 MΩ cm resistance and conforming to Specification D1193.
satisfactory baseline separation of the anion peak of interest as 14.3 Quartz Wool—(fine grade) or other suitable absorbent
shown in Fig. 1. material can be used that is stable and capable of withstanding
13.11.7 Anion Suppressor Device, reduces the background temperatures inside the furnace.
conductivity of the eluent after separation by the anion NOTE 7—Materials meeting the requirements in 8.4 provide a more
separator column. Both chemical and continuous electrolytic 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
suppressors have been found satisfactory for this method. of the sample into the furnace. Consult instrument manufacturer recom-
Other anion suppressor devices can be used as long as the mendations for further guidance.
precision and accuracy of the method are not degraded.
14.4 Argon or Helium, carrier gas minimum 99.99 % purity.
13.11.8 Conductivity Detector, temperature controlled to NOTE 8—Purification scrubbers to ensure the removal of containments
0.01 °C, capable of at least 0 µS ⁄cm to 15 000 µS ⁄cm on a such as moisture (molecular sieve) and hydrocarbon trap filters (activated
linear scale. charcoal or equivalent) are recommended.
13.11.9 Data Acquisition System, an integrator or computer 14.5 Oxygen, combustion gas minimum 99.75 % purity.
data handling system capable of integrating the peak areas of
the ion chromatograph. 14.6 Calibration Standards, certified calibration standards
from commercial sources or calibration standards prepared in
13.12 Quartz or Ceramic Sample Boats, of sufficient size to the laboratory containing the elements or anions at the concen-
hold 10 µL to 100 µL. The boat is filled with quartz wool or trations of interest.
other suitable material (8.4) to wick any remaining drops of the 14.6.1 1-Chloropentane, FW 106.59, 33.2% Cl.
sample from the tip of the syringe needle prior to introduction 14.6.2 Organic Chloride Standard, Chloropentane (FW
of the sample into the furnace. 106.59, 33.2% Cl) diluted in isooctane has been used success-
13.13 Volumetric Flasks–Type Class A, in accordance with fully for chloride calibration. Other sources of organic chloride
Specification E288 at the volume required for the preparation can be used as long as performance, precision, and accuracy
of standards, reagents, and solutions. are not degraded.

FIG. 1 Anion Peak of Interest (Chloride)

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 D8150 − 17
NOTE 9—Calibration standards can have a useful shelf life of about P = % purity of target standard compounds listed in 14.6.1,
three months if properly stored in a cool, dark place.
NOTE 10—A correction for chemical impurity can be used if deemed
and
necessary. K = 106 (correction factor to convert g/mL to µg/mL).
14.7 Eluent Solution—Follow the specific guidelines for the 14.11 Absorption Solution—Type I water conforming to
preparation and use of the eluent solution from the manufac- Specification D1193.
turer of the columns being used. Other concentrations can be 14.12 Working Standard Solution—Calculate the correct
used if precision and accuracy of the method is not degraded. concentrations obtained from the stock standard solution in
The solutions recommended by the column manufacturer can 14.10 and prepare a working standard by diluting the stock
be purchased from qualified vendors as long as the standard solution with solvent (14.9).
performance, precision, and accuracy are not degraded (see 14.12.1 Prepare a 50.0 µg/mL working standard by using a
Section 15 regarding Hazards). 5.0 mL Type Class A volumetric pipet (Specification E969) and
14.8 Suppressor Solutions: pipet 5.0 mL of the 1000 µg/mL stock standard solution(s)
14.8.1 Chemical Suppressor Regenerant Solution—Follow (14.10) into a 100 mL Type Class A volumetric flask (Speci-
the specific manufacturer guidelines for the preparation and use fication E288) and dilute to mark with solvent (14.9).
of the suppressor solution. The manufacturer recommended 14.13 Calibration Standards—Prepare calibration standards
solutions can be purchased from qualified vendors as long as by diluting the working standard solution (14.12) to create
the performance, precision, and accuracy are not degraded. 0.5 µg ⁄mL, 1.0 µg ⁄mL, 5.0 µg ⁄mL, 10 µg ⁄mL, and 25 µg ⁄mL
14.8.2 Electrolytic Suppressor Current Setting—Follow the calibration standards by pipetting 1.0 mL, 2.0 mL, 10.0 mL,
specific guidelines for the current setting from the vendor of 20.0 mL, and 50.0 mL of working standard solution with the
the suppressor being used based upon the flow rate and eluent appropriate Class A volumetric pipets into five separate 100
concentration being used for the analysis. mL Class A volumetric flasks and dilute to the mark with
solvent (14.9). The calibration standards used to calibrate the
14.9 Solvent—The solvent of choice should be capable of
system will include the solvent (14.9) as zero, the working
dissolving the standard or sample. The solvent should contain
standard for the 50 µg/mL and encompass the following
less than 0.05 mg/kg of the elements or anions of interest. The
approximate concentrations of calibration standards: 0.0 µg ⁄m,
blank value shall be determined for each new bottle of solvent.
0.5 µg ⁄m, 1.0 µg ⁄m, 5.0 µg ⁄m, 10 µg ⁄m, 25 µg ⁄m, and
Suggested solvents include, but are not limited to, iso-octane,
50 µg ⁄mL. The volume of working standard, in mL, needed to
xylene, toluene, and methanol.
prepare a calibration standard is determined using the formula
14.10 Stock Standard Solution(s) of approximately 1000 in Eq 4.
µg/mL—Prepare a stock standard solution by accurately weigh-
Conc cal 3 Vol cal
ing to within 10 % of the target weight for the target standard Vol work , mL 5 (4)
Conc work
compound listed in 14.6.1 into a 100 mL Type Class A
volumetric flask. Dilute to volume with the selected solvent where:
listed in 14.9. Calculate the actual concentration of the stock Volwork = volume of working standard needed to prepare
standard solution(s) for the element by using the formula in Eq the desired calibration standard, mL,
3 with the actual recorded weight of the target compound used Conccal = concentration of calibration standard desired,
for each element. This stock standard solution can be further µg/mL,
diluted to other desired concentrations. Other suitable Volcal = volume of calibration standard desired, mL, and
materials, weights and volumes can be substituted in preparing Concwork = concentration of working standard, µg/mL.
stock standard solution(s) as long as the performance of the 14.13.1 A summary outlining the preparation of the calibra-
method is not degraded. tion standards is shown in Table 1.
NOTE 11—Stock standard solutions from commercial sources can be 14.13.2 Final dilution volumes can be calculated using the
used if the accuracy, precision, and performance criteria of the method are formula in Eq 4.
not degraded.
NOTE 12—Alternative volumes and concentrations of working and
14.10.1 1-Chloropentane, (Chlorine), 0.3007 g target
weight.
TABLE 1 Calibration Standards—Preparation from Working
14.10.2 Calculate the actual concentration of the stock Standard Solution
standard solution(s) for chloride using Eq 3 with the actual
Calibration Working Standard Solution Final
recorded weight of the target compound. Standards Diluted
Conc Conc Volume Volume
A 3B 3P (µg/mL) (mL)A
Stock standard solution,µg/mL 5 3 106 (3) (µg/mL) (mL)B
V 3K
25 50.0 50 100
10 50.0 20 100
where: 5.0 50.0 10 100
A = mass of the target compound in grams, g, 1.0 50.0 2.0 100
B = % concentration of the elements in the respective target 0.5 50.0 1.0 100
A
compounds listed in 14.6.1, B
Use Class A volumetric pipets or equivalent meeting Specification E969.
V = final diluted volume, mL, Use Class A volumetric flasks or equivalent meeting Specification E288.

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 D8150 − 17
calibration standards can be prepared so long as the preparation meets the 16.3 Adjust gas flows and pyrolysis temperatures to the
concentration range needed to properly bracket the response of the operating conditions as recommended by the instrument manu-
samples and adhere to the scope of the method.
NOTE 13—Working standard solutions should be prepared on a regular
facturer.
basis depending upon the frequency of use and age. The working standard
solution can be retained, if refrigerated, for up to three months. Do not 17. Calibration
refrigerate working standard solution if prepared in benzene as the
benzene will freeze and cause erratic results. 17.1 Prior to the analysis of standards or samples, it is
NOTE 14—Alternatively, calibration standards can be prepared by necessary to run a series of system blanks (17.1.1) and solvent
gravimetric dilution provided the same solvents are used throughout. The blanks (17.1.2) to ensure cleanliness of the system. Follow the
solvent used for the stock standard solution, working standard and
manufacturer’s recommendation for this process.
calibration standards shall all be the same. In this case, the final
concentration unit for the calibration standards will remain µg/mL even 17.1.1 A system blank consists of a combustion ion chro-
though the dilutions were performed gravimetrically. matography (CIC) analysis with no solvent or sample injection
in which the same combustion, chromatography and time
15. Hazards protocols are used as for the sample analysis, but without the
15.1 Consult the current version of OSHA regulations, combustion of a sample or solvent blank. The system blank
supplier’s Safety Data Sheets (SDS), and local regulations for shall be equal to or less than 50 % (1⁄2) the area counts of the
all materials used in this test method. lowest calibration standard used for calibration.
15.2 High temperature and flammable hydrocarbons occur 17.1.2 A solvent blank consists of a combustion ion chro-
in the test method. Use materials that are rated for containing matography (CIC) analysis of the solvent used for preparation
these hydrocarbons in all sample containers and sample trans- of the calibration standards in which the same combustion,
fer apparatus. Exercise extra care when using flammable chromatography, and time protocols are used for the sample
materials near the oxidative furnace. analysis. The solvent blank area count shall be equal to or less
than 50 % (1⁄2) the area counts of the lowest calibration
15.3 Potassium hydroxide is a caustic alkali, which in an
standard used for calibration.
anhydrous or strong solution forms, is a hazardous material. In
contact with the skin, it produces burns that can be quite 17.1.3 The series of system blanks should be analyzed
serious unless promptly treated. Its action is insidious since it repeatedly until a stable baseline response is achieved.
produces no immediate stinging or burning sensation and Typically, 3 to 5 system blanks will be required following
damage to the skin can result before its presence is realized. start-up of the instrument. A stable background is considered
Eyes are particularly vulnerable to severe damage from alkalis. achieved when the analysis of a minimum of two consecutive
system blanks have area counts equal to or less than 15 %
15.4 Use safety goggles or face shields and rubber gloves relative difference for the anions of interest. If a stable baseline
when handling alkalis and avoid spillage on clothing. These response is not obtained, follow the manufacturer’s recommen-
materials rapidly attack wool and leather. dations to check for sources of contamination.
15.5 Use all appropriate safety precautions to clean up and
17.2 Prepare a series of calibration standards covering the
discard in accordance with all federal, state, and local health
range of samples to be analyzed by diluting the working
and environmental regulations.
standard (14.12) prepared from the stock standard solution
16. Preparation of Apparatus (14.10) to the desired final concentrations.
NOTE 15—Commercially available standards can be used as long as the
16.1 Set up the instrument in accordance with the manufac- accuracy and precision of the method is not degraded.
turer’s instructions. A typical diagram of a CIC system is
shown in Fig. 2. 17.3 Analyze the calibration standards covering the analyti-
cal range of the samples and determine the peak areas
16.2 Set instrument parameters in accordance with the corresponding to the chloride ion. The use of an automated
manufacturer’s instructions. sampling device is required to ensure accurate and repeatable
injection volumes and techniques.
17.4 An aliquot of absorbing solution following the com-
bustion of each standard is introduced into the IC for separation
and quantification. Retention times vary with operating condi-
tions. The standards, therefore, shall be analyzed by the IC in
the same manner as the sample solutions. Consult the manu-
facturer’s recommendations for analyte elution order.
17.5 After the standards have been analyzed, a calibration
curve is determined using a “best-fit” regression by plotting
concentration versus the integrated instrument response (peak
area) for chloride. Instrument response is calculated and
defined per the manufacturer’s recommendations. A typical
calibration includes a series of four or more standards contain-
FIG. 2 Combustion IC Diagram ing the elements of interest and bracketing the concentrations

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 D8150 − 17
that are in the samples. The calibration curve should have a 20.2 The organic chloride content of the original crude oil
correlation coefficient (r2) greater than 0.995. sample specimen is also expressed as µg/g. and shall reference
this test method.
18. Procedure
20.3 Should a modification be employed with a pre-water
18.1 Obtain a naphtha specimen using the procedure de- wash, as discussed in Appendix X2, make note on the report
scribed in Section 11. The concentrations in the naphtha with “D8150 Modified with Crude Pre-wash”.
specimen shall be less than the concentration of the highest
calibration standard and greater than the lowest calibration 21. Quality Assurance/Quality Control (QA/QC)
standard used in the calibration. If required, a dilution of the
sample can be performed. 21.1 Confirm the performance of the instrument and the test
procedure by analyzing a QC sample.
18.2 Analyze the samples using identical instrument condi- 21.1.1 When QA/QC protocols are already established in
tions as used for calibration. the testing facility, these can be used when they confirm the
18.3 Inspect the combustion tube and other flow path reliability of test result.
components to verify complete oxidation of the test specimen 21.1.2 When there is no QA/QC protocol established in the
after analysis. testing facility, Appendix X1 can be used as the QA/QC
18.4 If necessary, increase the residence time for the boat in system.
the furnace if coke or soot is observed on the boat after 21.2 Users of this test method are advised that in contractual
combustion. Decrease the boat drive introduction rate or hold agreements, one or more of the contracting parties can and can
times in the furnace, or both, if coke or soot is observed on the make Appendix X1 mandatory practice.
exit end of the combustion tube.
18.5 Clean any coke or soot as per the manufacturer’s 22. Precision and Bias5
instructions. After any cleaning or adjustment, assemble and 22.1 Precision—The precision of these test methods as
leak check the apparatus. Run a check standard to determine if determined by the statistical examination of the interlaboratory
the instrument needs to be recalibrated. test results is as follows:
22.1.1 Repeatability—The difference between successive
19. Calculation results obtained by the same operator with the same apparatus
19.1 If the combustion ion chromatograph has a computer- under constant operating conditions on identical test materials
based data handling software, follow manufacturer procedures would, in the long run, in the normal and correct operation,
for calculation of chloride concentration in the naphtha fraction exceed the following values only in 5 % of the cases (one case
in units of µg/mL. in twenty).
19.2 For analyzers calibrated manually, calculate the con- 22.1.1.1 Values can be obtained for organically-bound chlo-
centration of chloride in the absorber solution, in units of rine for any given concentration above 1 µg ⁄g (in the original
µg/mL, using the peak area obtained from the sample and the crude oil specimen) using Eq 6 as follows:
calibration curve(s) generated in Section 17. Calculate the repeatability, r 5 0.2918~ X ! 0.6746 (6)
concentration of chloride in the naphtha fraction using the
where:
formula in Eq 5.
X = µg/g chloride.
C Abs 3 V Abs
Chloride, µg/g 5 3 1000 (5) 22.1.1.2 Calculated recovery values using the repeatability
V inj 3 D
definition for this method, described in Section 22.1.1.1, are
where: shown in Table 2.
CAbs = concentration of chloride in the absorption solution,
µg/mL,
VAbs = final volume of absorption solution, mL,
Vinj = volume of absorption solution analyzed (injected),
5
µL, Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1868. Contact ASTM Customer
D = density of test specimen, mg/µL (equivalent to g/mL, Service at [email protected].
see 12.2), and
1000 = factor to convert mass of sample injected from
TABLE 2 Calculated Precision Values
milligrams to grams.
Cl, µg/g repeatability r, µg/g Reproducibility R, µg/g
19.3 The concentration of organic chloride in the original 1.0 0.29 0.76
crude oil sample specimen can be obtained by multiplying the 2.0 0.47 1.2
chloride concentration in the naphtha fraction (see 19.1 or 3.0 0.61 1.6
4.0 0.74 1.9
19.2) by the naphtha fraction, f (see 12.1). 5.0 0.86 2.3
6.0 0.98 2.5
20. Report 8.0 1.2 3.1
10 1.4 3.6
20.1 Report the organic chloride content of the naphtha 12 1.6 4.1
fraction in µg/g calculated in Section 19.

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 D8150 − 17
22.1.2 Reproducibility—The difference between two single 22.2 Bias—Since no generally accepted standard reference
and independent results obtained by different operators work- materials with known values of organic chlorides in crude oil
ing in different laboratories on identical material would, in the are available, bias of this test method cannot be determined.
long run, exceed the following values only in 5 % of the cases
(one case in twenty). 23. Keywords
22.1.2.1 Values can be obtained for organically-bound chlo-
23.1 analysis; anions; aromatics; chloride; chlorine; CIC;
rine for any given concentration above 1 µg ⁄g (in the original
crude oil specimen) using Eq 7 as follows: combustion; combustion ion chromatography; crude oil; hy-
drolysis; ion chromatography; organic chloride; organo-
Reproducibility, R 5 0.7599~ X ! 0.6746 (7) chlorine; organic halides ; oxidative pyrohydrolytic combus-
where: tion; pyrohydrolytic
X = µg/g chloride.
22.1.2.2 Calculated recovery values using the Reproducibil-
ity definition for this method, described in Section 22.1.2.1, are
shown in Table 2.

APPENDIXES

(Nonmandatory Information)

X1. GENERIC QUALITY CONTROL STATEMENT FOR D02 TEST METHODS

X1.1 Confirm the performance of the instrument and the test criticality of the quality being measured, the demonstrated
procedure by analyzing a QC sample. stability of the testing process, and customer requirements.
Generally, a QC sample should be analyzed on each day of
X1.2 Prior to monitoring the measurement process, the user
testing routine samples. The QC frequency should be increased
of the test method needs to determine the average value and
control limits of the QC sample (see Practice D6299 and when a large number of samples are routinely analyzed.
MNL76). However, when it is demonstrated that the testing is under
statistical control, the QC testing frequency can be reduced.
X1.3 Record the QC results and analyze by control charts or The QC sample precision should be periodically checked
other statistically equivalent techniques to ascertain the statis- against the ASTM test method precision to ensure data quality.
tical control status of the total testing process (see Practice
D6299 and MNL7). Any out-of-control data should trigger X1.5 It is recommended that, when possible, the type of QC
investigation for root cause(s). The results of this investigation sample that is regularly tested be representative of the samples
can, but not necessarily, result in instrument recalibration. routinely analyzed. An ample supply of QC sample material
X1.4 In the absence of explicit requirements given in the should be available for the intended period of use and shall be
test method, the frequency of QC testing is dependent on the homogeneous and stable under the anticipated storage condi-
tions.
6
MNL7, Manual of Presentation of Data Control Chart Analysis, 6th ed.,
Section 3: Control Chart for Individuals, ASTM International, W. Conshohocken, X1.6 See Practice D6299 and MNL7 for further guidance
PA. on QC and control charting techniques.

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 D8150 − 17

X2. CAUTION REGARDING CRUDE OIL SAMPLE PREPARATION USING WATER WASHING

X2.1 Under certain conditions, salt (inorganic chlorides salts prior to analysis can provide “false negative” results when
such as MgCl2 and CaCl2) contained within many crude oils considering refinery operations. The user of the method should
can undergo hydrolysis during the D86 distillation step used to consider how the data is to be used before choosing to
isolate the <204 °C fraction for analysis. The hydrolysis results implement a pre-distillation water wash. It is advised to
in the formation of hydrochloric acid (HCl), which can conduct the method as written, without pre-distillation wash.
subsequently react with available organic chloride precursors Then, if deemed necessary, conduct the evaluation with the
such as olefins, alcohols and esters that are present in the pre-distillation water wash in place, and report both results.
naphtha fraction, and form organic chlorides. These formed
organic chlorides remain in the naphtha fraction and are X2.3 In the event that a sample was prepared for testing by
reported in the final test result. As a result, some users have water washing the neat crude, the reported results shall include
adopted the practice of water washing neat crude samples prior the following statement indicating what sample preparation
to distillation, in order to remove what is often deemed a technique was employed. “D8150-Modified with Crude Pre-
potential interference. Wash.” When a pre-distillation water wash modification is
employed, the published precision may not apply.
X2.2 This crude oil sample preparation practice has the
potential to bias the final test results since the act of distillation X2.4 While this method permits water washing of the
simulates the conditions of an atmospheric crude distillation distilled naphtha, it does not include neat sample preparation
tower. Any organic chlorides that are present in the naphtha by water washing of the crude oil sample prior to testing, and
pose a risk to refinery operations therefore their presence or the information provided in this appendix should not be
absence in the test results are relevant. Removal of inorganic interpreted as support for this preparation practice.

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