ASTM D4929-07(2014)
(Test Method)Standard Test Methods for Determination of Organic Chloride Content in Crude Oil
Standard Test Methods for Determination of Organic Chloride Content in Crude Oil
SIGNIFICANCE AND USE
4.1 Organic chloride species are potentially damaging to refinery processes. Hydrochloric acid can be produced in hydrotreating 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.
SCOPE
1.1 These test methods cover the determination of organic chloride (above 1 μg/g organically-bound chlorine) in crude oils, using either distillation and sodium biphenyl reduction or distillation and microcoulometry.
1.2 These test methods involve 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 5 regarding potential interferences.
1.3 Test Method A covers the determination of organic chloride in the washed naphtha fraction of crude oil by sodium biphenyl reduction followed by potentiometric titration.
1.4 Test Method B covers the determination of organic chloride in the washed naphtha fraction of crude oil by oxidative combustion followed by microcoulometric titration.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard. The preferred concentration units are micrograms of chloride per gram of sample.
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 and health practices and determine the applicability of regulatory limitations prior to use.
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Designation: D4929 − 07(Reapproved 2014)
Standard Test Methods for
Determination of Organic Chloride Content in Crude Oil
This standard is issued under the fixed designation D4929; 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 D4177 Practice for Automatic Sampling of Petroleum and
Petroleum Products
1.1 These test methods cover the determination of organic
D6299 Practice for Applying Statistical Quality Assurance
chloride (above 1 µg/g organically-bound chlorine) in crude
and Control Charting Techniques to Evaluate Analytical
oils, using either distillation and sodium biphenyl reduction or
Measurement System Performance
distillation and microcoulometry.
1.2 These test methods involve the distillation of crude oil
3. Summary of Test Method
test specimens to obtain a naphtha fraction prior to chloride
3.1 A crude oil distillation is performed to obtain the
determination. The chloride content of the naphtha fraction of
naphtha cut at 204°C (400°F). The distillation method was
the whole crude oil can thereby be obtained. See Section 5
adaptedfromTestMethodD86forthedistillationofpetroleum
regarding potential interferences.
products. The naphtha cut is washed with caustic, repeatedly
1.3 Test Method A covers the determination of organic
when necessary, until all hydrogen sulfide is removed. The
chloride in the washed naphtha fraction of crude oil by sodium
naphtha cut, free of hydrogen sulfide, is then washed with
biphenyl reduction followed by potentiometric titration.
water, repeatedly when necessary, to remove inorganic halides
1.4 Test Method B covers the determination of organic
(chlorides).
chloride in the washed naphtha fraction of crude oil by
3.2 There are two alternative test methods for determination
oxidative combustion followed by microcoulometric titration.
of the organic chloride in the washed naphtha fraction, as
1.5 The values stated in SI units are to be regarded as
follows.
standard. No other units of measurement are included in this
3.2.1 Test Method A, Sodium Biphenyl Reduction and
standard. The preferred concentration units are micrograms of
Potentiometry—The washed naphtha fraction of a crude oil
chloride per gram of sample.
specimen is weighed and transferred to a separatory funnel
1.6 This standard does not purport to address all of the
containing sodium biphenyl reagent in toluene. The reagent is
safety concerns, if any, associated with its use. It is the
an addition compound of sodium and biphenyl in ethylene
responsibility of the user of this standard to establish appro-
glycol dimethyl ether. The free radical nature of this reagent
priate safety and health practices and determine the applica-
promotes very rapid conversion of the organic halogen to
bility of regulatory limitations prior to use.
inorganic halide. In effect this reagent solubilizes metallic
sodium in organic compounds. The excess reagent is
2. Referenced Documents
decomposed, the mixture acidified, and the phases separated.
2.1 ASTM Standards:
The aqueous phase is evaporated to 25 to 30 mL, acetone is
D86 Test Method for Distillation of Petroleum Products at
added, and the solution titrated potentiometrically.
Atmospheric Pressure
3.2.2 Test Method B, Combustion and Microcoulometry
D1193 Specification for Reagent Water
—The washed naphtha fraction of a crude oil specimen is
D4057 Practice for Manual Sampling of Petroleum and
injected into a flowing stream of gas containing about 80 %
Petroleum Products
oxygen and 20 % inert gas, such as argon, helium, or nitrogen.
The gas and sample flow through a combustion tube main-
tained at about 800°C. The chlorine is converted to chloride
These test methods are under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and are the direct responsibility
and oxychlorides, which then flow into a titration cell where
of Subcommittee D02.03 on Elemental Analysis.
they react with the silver ions in the titration cell. The silver
CurrenteditionapprovedMay1,2014.PublishedJuly2014.Originallyapproved
ions thus consumed are coulometrically replaced. The total
in 1989. Last previous edition approved in 2007 as D4929 – 07. DOI: 10.1520/
D4929-07R14. current required to replace the silver ions is a measure of the
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
chlorine present in the injected samples.
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
3.2.3 The reaction occurring in the titration cell as chloride
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. enters is as follows:
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4929 − 07 (2014)
2 1
Cl 1Ag →AgCl s (1) 7.2 Tee Adapter, borosilicate, 75° angle side-arm, 24/40
~ !
ground-glass joints.
3.2.4 The silver ion consumed in the above reaction is
7.3 Thermometer, ASTM thermometer 2C (–5 to 300°C) or
generated coulometrically thus:
2F, (20°F to 580°F).
1 2
Ag°→Ag 1e (2)
7.3.1 Othertemperaturemeasuringdevices,suchasthermo-
3.2.5 These microequivalents of silver are equal to the
couples or resistance thermometers, may be used when the
number of microequivalents of titratable sample ion entering
temperature reading obtained by these devices is determined to
the titration cell.
produce the same naphtha fraction that is obtained when
mercury-in-glass thermometers are used.
4. Significance and Use
7.4 Thermometer Adapter, borosilicate, 24/40 inner ground-
4.1 Organic chloride species are potentially damaging to
glass joint.
refinery processes. Hydrochloric acid can be produced in
7.5 Liebig Condenser, borosilicate, 300-mm length, 24/40
hydrotreatingorreformingreactorsandtheacidaccumulatesin
ground-glass joints.
condensing regions of the refinery. Unexpected concentrations
7.6 Vacuum Take-Off Adapter,borosilicate,105°anglebend,
of organic chlorides cannot be effectively neutralized and
damage can result. Organic chlorides are not known to be 24/40 ground-glass joints.
naturally present in crude oils and usually result from cleaning
7.7 Receiving Cylinder, borosilicate, 250-mL capacity,
operationsatproducingsites,pipelines,ortanks.Itisimportant
24/40 outer ground-glass joint.
for the oil industry to have common methods available for the
7.8 Wire Clamps, for No. 24 ground-glass joints, stainless
determination of organic chlorides in crude oil, particularly
steel.
when transfer of custody is involved.
7.9 Receiver Flask, for ice bath, 4 L.
5. Interferences
7.10 Copper Tubing, for heat exchanger to cool condenser
5.1 Test Method A—Other titratable halides will also give a
water, 6.4-mm outside diameter, 3-m length.
positive response. These titratable halides include HBr and HI.
7.11 Electric Heating Mantle, Glas-Col Series 0, 1-L size,
5.2 Test Method B—Other titratable halides will also give a
140-W upper heating element, 380-W lower heating element.
positive response. These titratable halides include HBr and HI
7.12 Variacs, 2, for temperature control of upper and lower
(HOBr and HOI do not precipitate silver). Since these oxyha-
heating elements, 120 V, 10 amps.
lides do not react in the titration cell, approximately 50 %
microequivalent response is detected.
8. Reagents and Materials
5.2.1 This test method is applicable in the presence of total
8.1 Acetone, chloride-free. (Warning—Extremely
sulfur concentration of up to 10 000 times the chlorine level.
flammable, can cause flash fires. Health hazard.)
6. Purity of Reagents
8.2 Caustic Solution, 1 M potassium hydroxide
(Warning—Can cause severe burns to skin.) prepared in
6.1 Purity of Reagents—Reagent grade chemicals shall be
distilled/deionized water.
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit-
8.3 Distilled/Deionized Water.
tee onAnalytical Reagents of theAmerican Chemical Society,
8.4 Filter Paper, Whatman No. 41 or equivalent.
where such specifications are available. Other grades may be
4,5
8.5 Stopcock Grease.
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
8.6 Toluene, chloride-free. (Warning—Flammable. Health
accuracy of the determination.
hazard.)
6.2 Purity of Water—Unless otherwise indicated, references
9. Sampling
to water shall be understood to mean reagent water as defined
by Type III of Specification D1193. 9.1 Obtain a test unit in accordance with Practice D4057 or
D4177. To preserve volatile components, which are in some
DISTILLATION AND CLEANUP PROCEDURE
samples, do not uncover samples any longer than necessary.
Samples should be analyzed as soon as possible, after taking
7. Apparatus
from bulk supplies, to prevent loss of organic chloride or
7.1 Round-Bottom Boiling Flask, borosilicate, 1 L, single
contamination due to exposure or contact with sample con-
short neck with 24/40 outer ground-glass joint.
tainer. (Warning—Samples that are collected at temperatures
3 4
Reagent Chemicals, American Chemical Society Specifications, American The sole source of supply of the stop-cock grease known to the committee at
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not this time is Dow Corning silicone, available from Dow Corning Corporation,
listed by the American Chemical Society, see Annual Standards for Laboratory Corporate Center, PO Box 994, Midland, MI.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia If you are aware of alternative suppliers, please provide this information to
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, ASTM International Headquarters. Your comments will receive careful consider-
MD. ation at a meeting of the responsible technical committee, which you may attend.
D4929 − 07 (2014)
below room temperature may undergo expansion and rupture 11.2 Transfer the naphtha fraction from the receiving cylin-
the container. For such samples, do not fill the container to the der to the separatory funnel. Using the separatory funnel, wash
top; leave sufficient air space above the sample to allow room the naphtha fraction three times with equal volumes of the
for expansion.) caustic solution (1 M KOH). Follow the caustic wash with a
water wash, again washing three times with equal volumes.
9.2 If the test unit is not used immediately, then thoroughly
The caustic wash removes hydrogen sulfide, while the water
mix in its container prior to taking a test specimen. Some test
wash removes traces of inorganic chlorides either originally
units can require heating to thoroughly homogenize.
present in the crude or from impurities in the caustic solution.
(Warning—When heating is required, care should be taken so
After the washings are complete, filter the naphtha fraction to
that no organic chloride containing hydrocarbons are lost.)
remove residual freestanding water. Store the naphtha fraction
in a clean glass bottle. This naphtha fraction can now be
10. Preparation of Apparatus
analyzed for organic chlorides by either sodium biphenyl or
10.1 Clean all glassware by rinsing successively with tolu-
combustion/microcoulometric techniques.
ene and acetone.After completing the rinse, dry the glassware
11.3 Measure the density of the crude oil specimen and the
using a stream of dry nitrogen gas. Obtain and record the
naphtha fraction by obtaining the mass of 10.0 mL (using a
masses of the round-bottom flask and receiving cylinder.
10-mL volumetric flask) of each to the nearest 0.1 g.
Assembletheglassdistillationapparatususingstopcockgrease
to seal all joints and wire clamps to prevent loosening of the
12. Calculation
joints. Adjust the thermometer position within the adapter tee
12.1 Calculate naphtha fraction as follows:
suchthatthelowerendofthecapillaryislevelwiththehighest
f 5 M /M (3)
point on the bottom of the inner wall of the adapter tee section
n c
that connects to the condenser.
where:
NOTE 1—A diagram illustrating the appropriate positioning of the
f = mass fraction of naphtha collected,
thermometer can be found in Test Method D86.
M = mass of naphtha collected, and
n
M = mass of crude oil specimen.
10.2 Form the copper tubing into a coil to fit inside the
c
receiver flask, leaving room in the center of the flask for the
12.2 Calculate the density as follows:
receiving cylinder. With the PVC tubing, connect one end of
Density, g/mL 5 m/v (4)
the copper coil to the water source, and connect the other end
of the coil to the lower fitting of the Liebig condenser cooling
where:
jacket. Connect the upper condenser fitting to the water drain.
m = mass of sample specimen, g, and
Fillthereceiverflaskwithanice/watermixture,andturnonthe
v = volume of sample specimen, mL.
water. Maintain the temperature of the condenser below 10°C.
TEST METHOD A—SODIUM BIPHENYL
REDUCTION AND POTENTIOMETRY
11. Procedure
11.1 Add a 500-mL crude oil test specimen to tared round
13. Apparatus
bottom flask. Obtain and record the mass of the crude oil-filled
13.1 Electrodes—Thecleaningandpropercareofelectrodes
flask to the nearest 0.1 g. Connect the flask to the distillation
are critical to the accuracy of this test. Manufacturer’s instruc-
apparatus. Place the heating mantle around the flask, and
tions for the care of electrodes shall be followed.
support the heating mantle/flask from the bottom. Connect the
13.1.1 Glass, general purpose. When glass electrodes are in
heating mantle to the variacs. Turn on the variacs and start the
continuous use, weekly cleaning with chrome-sulfuric acid
distillation. During the distillation, adjust the variac settings to
(Warning—Strong oxidizer; can cause severe burns; recog-
give a distillation rate of approximately 5 mL/min. Continue
nized carcinogen), or other strongly oxidizing cleaning
thedistillationuntilathermometerreadingof204°C(400°F)is
solution, is recommended.
attained.Whenthetemperaturereaches204°C(400°F),endthe
13.1.2 Silver-Silver Chloride, billet-type.
distillation by first disconnecting and removing the receiving
13.2 Titrator, potentiometric. The titrator is equipped with a
cylinder. After the receiving cylinder has been removed, turn
5-mL or smaller buret and a magnetic stirring motor.
off the variacs and remove the heating mantle from the flask.
Obtain and record the mass of the receiving cylinder and
14. Reagents and Materials
distillate.
11.1.1 The precision and bias statements were determined 1
...
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: D4929 − 07 D4929 − 07 (Reapproved 2014)
Standard Test Methods for
Determination of Organic Chloride Content in Crude Oil
This standard is issued under the fixed designation D4929; 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 These test methods cover the determination of organic chloride (above 1 μg/g organically-bound chlorine) in crude oils,
using either distillation and sodium biphenyl reduction or distillation and microcoulometry.
1.2 These test methods involve 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 5 regarding
potential interferences.
1.3 Test Method A covers the determination of organic chloride in the washed naphtha fraction of crude oil by sodium biphenyl
reduction followed by potentiometric titration.
1.4 Test Method B covers the determination of organic chloride in the washed naphtha fraction of crude oil by oxidative
combustion followed by microcoulometric titration.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
The preferred concentration units are micrograms of chloride per gram of sample.
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 and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D86 Test Method for Distillation of Petroleum Products at Atmospheric Pressure
D1193 Specification for Reagent Water
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
3. Summary of Test Method
3.1 A 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. 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).
3.2 There are two alternative test methods for determination of the organic chloride in the washed naphtha fraction, as follows.
3.2.1 Test Method A, Sodium Biphenyl Reduction and Potentiometry—The washed naphtha fraction of a crude oil specimen is
weighed and transferred to a separatory funnel containing sodium biphenyl reagent in toluene. The reagent is an addition
compound of sodium and biphenyl in ethylene glycol dimethyl ether. The free radical nature of this reagent promotes very rapid
conversion of the organic halogen to inorganic halide. In effect this reagent solubilizes metallic sodium in organic compounds. The
These test methods are under the jurisdiction of ASTM Committee D02 on Petroleum Products Products, Liquid Fuels, and Lubricants and are the direct responsibility
of Subcommittee D02.03 on Elemental Analysis.
Current edition approved Nov. 1, 2007May 1, 2014. Published December 2007July 2014. Originally approved in 1989. Last previous edition approved in 20042007 as
D4929D4929 – 07.–04. DOI: 10.1520/D4929-07.10.1520/D4929-07R14.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4929 − 07 (2014)
excess reagent is decomposed, the mixture acidified, and the phases separated. The aqueous phase is evaporated to 25 to 30 mL,
acetone is added, and the solution titrated potentiometrically.
3.2.2 Test Method B, Combustion and Microcoulometry —The washed naphtha fraction of a crude oil specimen is injected into
a flowing stream of gas containing about 80 % oxygen and 20 % inert gas, such as argon, helium, or nitrogen. The gas and sample
flow through a combustion tube maintained at about 800°C. The chlorine is converted to chloride and oxychlorides, which then
flow into a titration cell where they react with the silver ions in the titration cell. The silver ions thus consumed are coulometrically
replaced. The total current required to replace the silver ions is a measure of the chlorine present in the injected samples.
3.2.3 The reaction occurring in the titration cell as chloride enters is as follows:
2 1
Cl 1Ag →AgCl s (1)
~ !
3.2.4 The silver ion consumed in the above reaction is generated coulometrically thus:
1 2
Ag°→Ag 1e (2)
3.2.5 These microequivalents of silver are equal to the number of microequivalents of titratable sample ion entering the titration
cell.
4. Significance and Use
4.1 Organic chloride species are potentially damaging to refinery processes. Hydrochloric acid can be produced in hydrotreating
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.
5. Interferences
5.1 Test Method A—Other titratable halides will also give a positive response. These titratable halides include HBr and HI.
5.2 Test Method B—Other titratable halides will also give a positive response. These titratable halides include HBr and HI
(HOBr and HOI do not precipitate silver). Since these oxyhalides do not react in the titration cell, approximately 50 %
microequivalent response is detected.
5.2.1 This test method is applicable in the presence of total sulfur concentration of up to 10 000 times the chlorine level.
6. Purity of Reagents
6.1 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 may be used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
6.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water as defined by
Type III of Specification D1193.
DISTILLATION AND CLEANUP PROCEDURE
7. Apparatus
7.1 Round-Bottom Boiling Flask, borosilicate, 1 L, single short neck with 24/40 outer ground-glass joint.
7.2 Tee Adapter, borosilicate, 75° angle side-arm, 24/40 ground-glass joints.
7.3 Thermometer, ASTM thermometer 2C (–5 to 300°C) or 2F, (20°F to 580°F).
7.3.1 Other temperature measuring devices, such as thermocouples or resistance thermometers, may 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.
7.4 Thermometer Adapter, borosilicate, 24/40 inner ground-glass joint.
7.5 Liebig Condenser, borosilicate, 300-mm length, 24/40 ground-glass joints.
7.6 Vacuum Take-Off Adapter, borosilicate, 105° angle bend, 24/40 ground-glass joints.
7.7 Receiving Cylinder, borosilicate, 250-mL capacity, 24/40 outer ground-glass joint.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed by
the American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
D4929 − 07 (2014)
7.8 Wire Clamps, for No. 24 ground-glass joints, stainless steel.
7.9 Receiver Flask, for ice bath, 4 L.
7.10 Copper Tubing, for heat exchanger to cool condenser water, 6.4-mm outside diameter, 3-m length.
7.11 Electric Heating Mantle, Glas-Col Series 0, 1-L size, 140-W upper heating element, 380-W lower heating element.
7.12 Variacs, 2, for temperature control of upper and lower heating elements, 120 V, 10 amps.
8. Reagents and Materials
8.1 Acetone, chloride-free. (Warning—Extremely flammable, can cause flash fires. Health hazard.)
8.2 Caustic Solution, 1 M potassium hydroxide (Warning—Can cause severe burns to skin.) prepared in distilled/deionized
water.
8.3 Distilled/Deionized Water.
8.4 Filter Paper, Whatman No. 41 or equivalent.
4,5
8.5 Stopcock Grease.
8.6 Toluene, chloride-free. (Warning—Flammable. Health hazard.)
9. Sampling
9.1 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 may undergo expansion and rupture the container.
For such samples, do not fill the container to the top; leave sufficient air space above the sample to allow room for expansion.)
9.2 If the test unit is not used immediately, then thoroughly mix in its container prior to taking a test specimen. Some test units
can require heating to thoroughly homogenize. (Warning— When heating is required, care should be taken so that no organic
chloride containing hydrocarbons are lost.)
10. Preparation of Apparatus
10.1 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.
10.2 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.
11. Procedure
11.1 Add a 500-mL crude oil test specimen to 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.
11.1.1 The precision and bias statements were determined using mercury-in-glass thermometers only. Therefore, when alternate
temperature measuring devices are used, the cut-off temperature so obtained shall be that which will produce a naphtha cut similar
to what would be yielded when mercury-in-glass thermometers are used. Such alternate temperature measuring devices shall not
be expected to exhibit the same temperature lag characteristics as mercury-in-glass thermometers.
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.
D4929 − 07 (2014)
11.2 Transfer the naphtha fraction from the receiving cylinder to the 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 either sodium biphenyl or combustion/microcoulometric techniques.
11.3 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.
12. Calculation
12.1
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