ASTM D4929-Organic Chloride

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: D4929 − 19
Standard Test Method for

Determination of Organic Chloride Content in Crude Oil1
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* mendations issued by the World Trade Organization Technical

1.1 The procedures in this test method cover the determi- Barriers to Trade (TBT) Committee.
nation of organic chloride (above 1 µg/g organically-bound
chlorine) in crude oils, using either distillation and sodium 2. Referenced Documents
biphenyl reduction, distillation and microcoulometry, or distil- 2.1 ASTM Standards:2
lation and X-ray fluorescence (XRF) spectrometry. D86 Test Method for Distillation of Petroleum Products and
1.2 The procedures in this test method involve the distilla- Liquid Fuels at Atmospheric Pressure
tion of crude oil test specimens to obtain a naphtha fraction D1193 Specification for Reagent Water
prior to chloride determination. The chloride content of the D4057 Practice for Manual Sampling of Petroleum and
naphtha fraction of the whole crude oil can thereby be Petroleum Products
obtained. See Section 5 regarding potential interferences. D4177 Practice for Automatic Sampling of Petroleum and
Petroleum Products
1.3 Procedure A covers the determination of organic chlo- D6299 Practice for Applying Statistical Quality Assurance
ride in the washed naphtha fraction of crude oil by sodium and Control Charting Techniques to Evaluate Analytical
biphenyl reduction followed by potentiometric titration. Measurement System Performance
1.4 Procedure B covers the determination of organic chlo- D6300 Practice for Determination of Precision and Bias
ride in the washed naphtha fraction of crude oil by oxidative Data for Use in Test Methods for Petroleum Products and
combustion followed by microcoulometric titration. Lubricants
D6708 Practice for Statistical Assessment and Improvement
1.5 Procedure C covers the determination of organic chlo-
of Expected Agreement Between Two Test Methods that
ride in the washed naphtha fraction of crude oil by X-ray
Purport to Measure the Same Property of a Material
fluorescence spectrometry.
D7343 Practice for Optimization, Sample Handling,
1.6 The values stated in SI units are to be regarded as Calibration, and Validation of X-ray Fluorescence Spec-
standard. No other units of measurement are included in this trometry Methods for Elemental Analysis of Petroleum
standard. Products and Lubricants
1.6.1 The preferred concentration units are micrograms of
chloride per gram of sample, though milligrams of chloride per 3. Summary of Test Method
kilogram of sample is commonly used for Procedure C.
3.1 A crude oil distillation is performed to obtain the
1.7 This standard does not purport to address all of the naphtha cut at 204 °C (400 °F). The distillation method was
safety concerns, if any, associated with its use. It is the adapted from Test Method D86 for the distillation of petroleum
responsibility of the user of this standard to establish appro- products. The naphtha cut is washed with caustic, repeatedly
priate safety, health, and environmental practices and deter- when necessary, until all hydrogen sulfide is removed. The
mine the applicability of regulatory limitations prior to use. naphtha cut, free of hydrogen sulfide, is then washed with
1.8 This international standard was developed in accor- water, repeatedly when necessary, to remove inorganic halides
dance with internationally recognized principles on standard- (chlorides).
ization established in the Decision on Principles for the
3.2 There are three alternative procedures for determination
Development of International Standards, Guides and Recom-
of the organic chloride in the washed naphtha fraction, as
follows.
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
2
Subcommittee D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved July 1, 2019. Published August 2019. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1989. Last previous edition approved in 2017 as D4929 – 17. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D4929-19. the ASTM website.
*A Summary of Changes section appears at the end of this standard

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D4929 − 19
3.2.1 Procedure A, Sodium Biphenyl Reduction and 4.1.2.1 To ensure <1 mg ⁄kg organic chloride in the crude
Potentiometry—The washed naphtha fraction of a crude oil oil, the amount measured in the naphtha fraction shall be <1/f
specimen is weighed and transferred to a separatory funnel (where f is the naphtha fraction calculated with Eq 3).
containing sodium biphenyl reagent in toluene. The reagent is 4.1.3 Organic chloride present in the crude oil (for example,
an addition compound of sodium and biphenyl in ethylene methylene chloride, perchloroethylene, etc.) is usually distilled
glycol dimethyl ether. The free radical nature of this reagent into the naphtha fraction. Some compounds break down during
promotes very rapid conversion of the organic halogen to fractionation and produce hydrochloric acid, which has a
inorganic halide. In effect this reagent solubilizes metallic corrosive effect. Some compounds survive fractionation and
sodium in organic compounds. The excess reagent is are destroyed during hydro-treating (desulfurization of the
decomposed, the mixture acidified, and the phases separated. naphtha).
The aqueous phase is evaporated to 25 mL to 30 mL, acetone 4.2 Other halides can also be used for dewaxing crude oil; in
is added, and the solution titrated potentiometrically. such cases, any organic halides will have similar impact on the
3.2.2 Procedure B, Combustion and Microcoulometry—The refining operations as the organic chlorides.
washed naphtha fraction of a crude oil specimen is injected into
a flowing stream of gas containing about 80 % oxygen and 4.3 Organic chloride species are potentially damaging to
20 % inert gas, such as argon, helium, or nitrogen. The gas and refinery processes. Hydrochloric acid can be produced in
sample flow through a combustion tube maintained at about hydrotreating or reforming reactors and the acid accumulates in
800 °C. The chlorine is converted to chloride and oxychlorides, condensing regions of the refinery. Unexpected concentrations
which then flow into a titration cell where they react with the of organic chlorides cannot be effectively neutralized and
silver ions in the titration cell. The silver ions thus consumed damage can result. Organic chlorides are not known to be
are coulometrically replaced. The total current required to naturally present in crude oils and usually result from cleaning
replace the silver ions is a measure of the chlorine present in operations at producing sites, pipelines, or tanks. It is important
the injected samples. for the oil industry to have common methods available for the
3.2.3 The reaction occurring in the titration cell as chloride determination of organic chlorides in crude oil, particularly
enters is as follows: when transfer of custody is involved.
Cl2 1Ag1 →AgCl ~ s ! (1)
5. Interferences
3.2.4 The silver ion consumed in the above reaction is 5.1 Procedure A—Other titratable halides will also give a
generated coulometrically thus: positive response. These titratable halides include HBr and HI.
Ag°→Ag1 1e 2 (2) 5.2 Procedure B—Other titratable halides will also give a
3.2.5 These microequivalents of silver are equal to the positive response. These titratable halides include HBr and HI
number of microequivalents of titratable sample ion entering (HOBr and HOI do not precipitate silver). Since these oxyha-
the titration cell. lides do not react in the titration cell, approximately 50 %
3.2.6 Procedure C, X-ray Fluorescence Spectrometry—The microequivalent response is detected.
washed naphtha fraction of a crude oil specimen is placed in 5.2.1 This procedure is applicable in the presence of total
the X-ray beam, and the peak intensity of the chlorine Kα line sulfur concentration of up to 10 000 times the chlorine level.
is measured by monochromatic wavelength dispersive X-ray 5.3 Procedure C—X-ray fluorescence spectrometry tech-
fluorescence (MWDXRF), monochromatic energy dispersive niques may have interferences due to high sulfur content and
X-ray fluorescence (MEDXRF), or energy dispersive X-ray matrix effects due to differences in the carbon-hydrogen ratio.
fluorescence (EDXRF) spectrometry. The resulting net count- 5.3.1 Matrix effects result when the elemental composition
ing rate is then compared to a previously prepared calibration (excluding chlorine) of samples differs significantly from the
curve or equation to obtain the concentration of chlorine in standards, and significant errors in the chlorine determination
mg/kg. can result. For example, differences in the carbon-hydrogen
ratio of sample and calibration standards introduce errors in the
4. Significance and Use determination.
4.1 Organic chlorides do not occur naturally in crude oil. 5.3.2 In general, naphthas with compositions that vary from
When present, they result from contamination in some manner, white oils as specified in 27.1 can be analyzed with standards
such as disposal of chlorinated solvent used in many dewaxing made from base materials that are of the same or similar
pipeline or other equipment operations. composition. A base material for naphtha may be simulated by
4.1.1 Uncontaminated crude oil will contain no detectable mixing isooctane and toluene in a ratio that approximates the
organic chloride, and most refineries can handle very small expected aromatic content of the samples to be analyzed.
amounts without deleterious effects. 5.3.3 Naphtha samples may contain high amounts
4.1.1.1 Most trade contracts specify that no organic chloride (≥0.5 mass %) of sulfur leading to significant absorption of
is present in the crude oil. chlorine Kα radiation and low chlorine results. Such samples
4.1.2 Several pipelines have set specification limits at can, however, be analyzed using this test method provided
<1 mg ⁄kg organic chlorides in the whole crude, and <5 mg ⁄kg either that the calibration standards are prepared to match the
in the light naphtha, on the basis of the naphtha fraction being matrix of the sample or correction factors are applied to the
20 % of the original sample. results. In some cases, dilution of samples with sulfur-free and
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D4929 − 19
chlorine-free oil can be used to reduce the effect. The main 7.5 Liebig Condenser, borosilicate, 300 mm length, 24/40
disadvantage is, however, that dilution also lowers the amount ground-glass joints.
of chlorine in the specimen. Make sure that in the diluted 7.6 Vacuum Take-Off Adapter, borosilicate, 105° angle bend,
specimen, the chlorine content is higher than 1 mg ⁄kg before 24/40 ground-glass joints.
resorting to dilution.
5.3.4 Matrix matching requires the knowledge of typical 7.7 Receiving Cylinder, borosilicate, 250 mL capacity, 24/40
sulfur concentration in the naphtha sample and preparing outer ground-glass joint.
calibration standards, which contain a similar sulfur concen- 7.8 Wire Clamps, for No. 24 ground-glass joints, stainless
tration. This technique is not applicable for naphtha samples steel.
with an unknown or differing sulfur content than the calibration
samples. 7.9 Receiver Flask, for ice bath, 4 L.
5.3.5 Sulfur correction factors are typically applied by using 7.10 Copper Tubing, for heat exchanger to cool condenser
the software and algorithms supplied by the equipment vendor water, 6.4 mm outside diameter, 3 m length.
and typically uses one of the following forms: manual input of
7.11 Electric Heating Mantle, Glas-Col Series 0, 1 L size,
sulfur concentration followed by automatic correction, direct
140 W upper heating element, 380 W lower heating element.
measurement of sulfur followed by automatic correction,
correction by use of Compton scattering, and correction by 7.12 Variacs, 2, for temperature control of upper and lower
applying fundamental parameters. Follow manufacturer’s in- heating elements, 120 V, 10 amps.
structions for application of sulfur correction factors and when
to apply those factors. 8. Reagents and Materials
8.1 Acetone, chloride-free. (Warning—Extremely
6. Purity of Reagents
flammable, can cause flash fires. Health hazard.)
6.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that 8.2 Caustic Solution, 1 M potassium hydroxide
all reagents shall conform to the specifications of the Commit- (Warning—Can cause severe burns to skin.) prepared in
tee on Analytical Reagents of the American Chemical Society, distilled/deionized water.
where such specifications are available.3 Other grades may be 8.3 Distilled/Deionized Water.
used, provided it is first ascertained that the reagent is of
8.4 Filter Paper, Whatman No. 41 or equivalent.
sufficiently high purity to permit its use without lessening the
accuracy of the determination. 8.5 Stopcock Grease.4,5
6.2 Purity of Water—Unless otherwise indicated, references 8.6 Toluene, chloride-free. (Warning—Flammable. Health
to water shall be understood to mean reagent water as defined hazard.)
by Type III of Specification D1193.
9. Sampling
DISTILLATION AND CLEANUP PROCEDURE
9.1 Obtain a test unit in accordance with Practice D4057 or
7. Apparatus D4177. To preserve volatile components, which are in some
samples, do not uncover samples any longer than necessary.
7.1 Round-Bottom Boiling Flask, borosilicate, 1 L, single Samples should be analyzed as soon as possible, after taking
short neck with 24/40 outer ground-glass joint. from bulk supplies, to prevent loss of organic chloride or
7.2 Tee Adapter, borosilicate, 75° angle side-arm, 24/40 contamination due to exposure or contact with sample con-
ground-glass joints. tainer. (Warning—Samples that are collected at temperatures
7.3 Thermometer, ASTM thermometer 2C (–5 °C to 300 °C) below room temperature may undergo expansion and rupture
or 2F, (20 °F to 580 °F). the container. For such samples, do not fill the container to the
7.3.1 Other temperature measuring devices, such as thermo- top; leave sufficient air space above the sample to allow room
couples or resistance thermometers, may be used when the for expansion.)
temperature reading obtained by these devices is determined to 9.2 If the test unit is not used immediately, then thoroughly
produce the same naphtha fraction that is obtained when mix in its container prior to taking a test specimen. Some test
mercury-in-glass thermometers are used. units can require heating to thoroughly homogenize.
7.4 Thermometer Adapter, borosilicate, 24/40 inner ground- (Warning—When heating is required, care should be taken so
glass joint. that no organic chloride containing hydrocarbons are lost.)
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.
5
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, 1 which you may attend.
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D4929 − 19
10. Preparation of Apparatus in a clean glass bottle. This naphtha fraction can now be
10.1 Clean all glassware by rinsing successively with tolu- analyzed for organic chlorides by either sodium biphenyl,
ene and acetone. After completing the rinse, dry the glassware combustion/microcoulometric techniques, or X-ray fluores-
using a stream of dry nitrogen gas. Obtain and record the cence spectrometry.
masses of the round-bottom flask and receiving cylinder. 11.3 Measure the density of the crude oil specimen and the
Assemble the glass distillation apparatus using stopcock grease naphtha fraction by obtaining the mass of 10.0 mL (using a
to seal all joints and wire clamps to prevent loosening of the 10 mL volumetric flask) of each to the nearest 0.1 g.
joints. Adjust the thermometer position within the adapter tee
12. Calculation
such that the lower end of the capillary is level with the highest
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point on the bottom of the inner wall of the adapter tee section 12.1 Calculate naphtha fraction as follows:
that connects to the condenser. f 5 M n /M c (3)
NOTE 1—A diagram illustrating the appropriate positioning of the where:
thermometer can be found in Test Method D86.
f = mass fraction of naphtha collected,
10.2 Form the copper tubing into a coil to fit inside the Mn = mass of naphtha collected, and
receiver flask, leaving room in the center of the flask for the Mc = mass of crude oil specimen.
receiving cylinder. With the PVC tubing, connect one end of
12.2 Calculate the density as follows:
the copper coil to the water source, and connect the other end
of the coil to the lower fitting of the Liebig condenser cooling Density, g/mL 5 m/v (4)
jacket. Connect the upper condenser fitting to the water drain. where:
Fill the receiver flask with an ice/water mixture, and turn on the
m = mass of sample specimen, g, and
water. Maintain the temperature of the condenser below 10 °C. v = volume of sample specimen, mL.
11. Procedure PROCEDURE A—SODIUM BIPHENYL REDUCTION
11.1 Add a 500 mL crude oil test specimen to tared round AND POTENTIOMETRY
bottom flask. Obtain and record the mass of the crude oil-filled 13. Apparatus
flask to the nearest 0.1 g. Connect the flask to the distillation
13.1 Electrodes—The cleaning and proper care of electrodes
apparatus. Place the heating mantle around the flask, and
are critical to the accuracy of this test. Manufacturer’s instruc-
support the heating mantle/flask from the bottom. Connect the
tions for the care of electrodes shall be followed.
heating mantle to the variacs. Turn on the variacs and start the
13.1.1 Glass, general purpose. When glass electrodes are in
distillation. During the distillation, adjust the variac settings to
continuous use, weekly cleaning with chrome-sulfuric acid
give a distillation rate of approximately 5 mL ⁄min. Continue
(Warning—Strong oxidizer; can cause severe burns; recog-
the distillation until a thermometer reading of 204 °C (400 °F)
nized carcinogen), or other strongly oxidizing cleaning
is attained. When the temperature reaches 204 °C (400 °F), end
solution, is recommended.
the distillation by first disconnecting and removing the receiv-
13.1.2 Silver-Silver Chloride, billet-type.
ing cylinder. After the receiving cylinder has been removed,
turn off the variacs and remove the heating mantle from the 13.2 Titrator, potentiometric. The titrator is equipped with a
flask. Obtain and record the mass of the receiving cylinder and 5 mL or smaller buret and a magnetic stirring motor.
distillate. 14. Reagents and Materials
11.1.1 The precision and bias statements were determined
using mercury-in-glass thermometers only. Therefore, when 14.1 Acetone, chloride-free. (Warning—Extremely
alternate temperature measuring devices are used, the cut-off flammable, can cause flash fires. Health hazard.)
temperature so obtained shall be that which will produce a 14.2 Congo Red Paper.
naphtha cut similar to what would be yielded when mercury- 14.3 2,2,4, trimethyl pentane (isooctane), reagent grade.
in-glass thermometers are used. Such alternate temperature (Warning—Flammable. Health hazard.)
measuring devices shall not be expected to exhibit the same
temperature lag characteristics as mercury-in-glass thermom- 14.4 Nitric Acid, approximately 5 M. (Warning—
eters. Corrosive, causes severe burns.) Add 160 mL of concentrated
nitric acid to about 200 mL of water and dilute to 500 mL.
11.2 Transfer the naphtha fraction from the receiving cylin-
der to the separatory funnel. Using the separatory funnel, wash 14.5 2-Propanol, chloride-free. (Warning—Flammable.
the naphtha fraction three times with equal volumes of the Health hazard.)
caustic solution (1 M KOH). Follow the caustic wash with a 14.6 Silver Nitrate, 0.01 M, standard aqueous solution.
water wash, again washing three times with equal volumes. 14.7 Sodium Biphenyl Reagent5,6—This is packed in 0.5 oz
The caustic wash removes hydrogen sulfide, while the water French square bottles (hereafter referred to as vials). The entire
wash removes traces of inorganic chlorides either originally
present in the crude or from impurities in the caustic solution. 6
The sole source of supply of the sodium biphenyl reagent known to the
After the washings are complete, filter the naphtha fraction to committee at this time is Southwestern Analytical Chemicals, P.O. Box 485, Austin,
remove residual freestanding water. Store the naphtha fraction TX.

D4929 − 19
contents of one vial are used for each analysis. One vial 16.5 Cool the solution and add 100 mL of acetone. Titrate
contains 13 meq to 15 meq of active sodium. Store the sodium the solution potentiometrically with standard 0.01 M silver
biphenyl reagent in a cool storage area, but do not refrigerate. nitrate, using glass versus silver-silver chloride electrodes. If
Prior to using, warm the reagent to approximately 50 °C and an automatic titrator, such as a Metrohm, is available, use the
shake thoroughly to ensure a homogeneous liquid. semi-micro 5 mL piston buret. If the titration is carried out with
a manually-operated pH meter, use a 5 mL semi-micro buret
14.8 Toluene, chloride-free. (Warning—Flammable. Health
that can be estimated to three decimal places in millilitres.
hazard.)
16.6 Determine the endpoint for the manual titration by
15. Preparation of Apparatus plotting the data showing emf versus volume of silver nitrate
solution used. Determine the endpoint for the automatic titrator
15.1 Recoating Silver-Silver Chloride Electrodes—Clean
from the midpoint of the inflection of the titration curve.
the metal surfaces of a pair of silver-silver chloride electrodes
with mild detergent and scouring powder. Rinse the electrodes 16.7 Determine a blank for each group of test specimens by
in distilled water. Immerse the metallic tips in saturated using all of the reagents, including the sodium biphenyl, and
potassium chloride solution. Connect one electrode to the following all the operations of the analysis except that the
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positive pole of a 1.6 V battery and the other to the negative sample itself is omitted.
pole. Reverse the polarity for several intervals of a few seconds
each to alternately clean and recoat the receptor electrode 17. Calculation
(connected to the positive pole). When adequately coated, the
17.1 Calculate chloride concentration in the naphtha frac-
receptor electrode tip will turn violet in color. This results from
tion as follows:
the action of light on the fresh silver chloride.
~ A 2 B ! ~ M ! ~ 35 460!
Chloride, µg/g 5 (5)
16. Procedure W
16.1 Use extreme care to prevent contamination. Reserve all where:

glassware for the chloride determination. Rinse glassware with A = volume of titrant for the sample specimen, mL,
distilled water followed by acetone just prior to use. Avoid B = volume of titrant for the blank, mL,
using chlorine-containing stopcock greases such as chlorotrif- M = molarity of silver nitrate, and
luoroethylene polymer grease. W = mass of sample specimen, g.
16.2 Place 50 mL of toluene in a 250 mL separatory funnel 17.2 The concentration of organic chloride in the original
and add the contents of one vial of sodium biphenyl reagent. crude oil sample specimen can be obtained by multiplying the
Swirl to mix and add about 30 g, obtaining the mass to the chloride concentration in the naphtha fraction (see 17.1) by the
nearest 0.1 g of the washed naphtha fraction of crude oil naphtha fraction (see 12.1).
sample. Obtain the mass of the sample bottle to determine the
PROCEDURE B—COMBUSTION AND
exact amount taken. Stopper the separatory funnel and swirl to
MICROCOULOMETRY
mix the contents thoroughly. The solution or suspension that
results should be blue-green in color. When it is not, add more
18. Apparatus
sodium biphenyl reagent (one vial at a time) until the solution
or suspension is blue-green. 18.1 Combustion Furnace—The sample specimen is to be
oxidized in an electric furnace capable of maintaining a
16.3 Allow 10 min after mixing for the reaction to be
temperature of 800 °C to oxidize the organic matrix.
completed, then add 2 mL of 2-propanol and swirl gently with
the funnel unstoppered for a time until the blue-green color 18.2 Combustion Tube—Fabricated from quartz and con-
changes to white, indicating that no free sodium remains. structed so a sample, which is vaporized completely in the inlet
Stopper the funnel and rock it gently, venting pressure fre- section, is swept into the oxidation zone by an inert gas where
quently through the stopcock. Then add 20 mL of water and it mixes with oxygen and is burned. The inlet end of the tube
10 mL of 5 M nitric acid. Shake gently, releasing the pressure shall hold a septum for syringe entry of the sample and side
frequently through the stopcock. Test the aqueous phase with arms for the introduction of oxygen and inert gases. The center
Congo red paper. If the paper does not turn blue, add additional section is to be of sufficient volume to ensure complete
5 M nitric acid in 5 mL portions until the blue color is obtained. oxidation of the sample.
16.4 Drain the aqueous phase into another separatory funnel 18.3 Titration Cell—Containing a sensor-reference pair of
containing 50 mL of isooctane and shake well. Drain the electrodes to detect changes in silver ion concentration and a
aqueous phase into a 250 mL titration beaker. Make a second generator anode-cathode pair of electrodes to maintain constant
extraction of the isooctane phase with 25 mL of water that has silver ion concentration and an inlet for a gaseous sample from
been acidified with a few drops of 5 M nitric acid. Add this the pyrolysis tube. The sensor, reference, and anode electrodes
second extract to the 250 mL titration beaker. Evaporate the shall be silver electrodes. The cathode electrode shall be a
solution on a hot plate kept just below the boiling point of the platinum wire. The reference electrode resides in a saturated
liquid until 25 mL to 30 mL remains. Do not boil or evaporate silver acetate half-cell. The electrolyte contains 70 % acetic
to less than 25 mL as loss of chloride may occur. acid in water.

D4929 − 19
18.4 Microcoulometer, having variable gain and bias 19.10 Silver Acetate, powder purified for saturated reference
control, and capable of measuring the potential of the sensing- electrode.
reference electrode pair, and of comparing this potential with a
bias potential, and of applying the amplified difference to the 20. Preparation of Apparatus
working-auxiliary electrode pair so as to generate a titrant. The
20.1 Set up the analyzer in accordance with the equipment
microcoulometer output signal shall be proportional to the
manufacturer instructions.
generating current. The microcoulometer may have a digital
meter and circuitry to convert this output signal directly to 20.2 The typical operational conditions are as follows:
nanograms or micrograms of chloride. Reactant gas flow, O2 160 mL ⁄min
Carrier gas flow 40 mL ⁄min
18.5 Sampling Syringe—A microlitre syringe of 50 µL ca- Furnace temperature:
pacity capable of accurately delivering 5 µL to 50 µL of sample Inlet zone 700 °C
Center and outlet zones 800 °C
into the pyrolysis tube. A 3 in. or 6 in. (76.2 mm or 152.4 mm) Coulometer:
needle is recommended to reach the inlet zone of approxi- Bias voltage, mV 240 to 265
mately 500 °C in the combustion zone. Gain ca. 1200
18.6 A constant rate syringe pump or manual dispensing 20.3 Optimize the bias voltage setting for the titration cell
adaptor may be used to facilitate slow injection of the sample null-point by injecting 30 µL of chloride-free water directly
into the combustion tube. It is recommended that the injection into the titration cell using a 6 in. needle. Adjust bias up or
rate not exceed 0.5 µL ⁄s. down to minimize the total integrated value due to this dilution
effect.
19. Reagents and Materials
21. Procedure
19.1 Acetic Acid, glacial acetic acid. (Warning—Corrosive,
21.1 Fill a 50 µL syringe with about 30 µL to 40 µL of the
causes severe burns.)
sample of washed naphtha fraction of crude oil, being careful
19.2 Argon, Helium, Nitrogen, or Carbon Dioxide, high to eliminate bubbles. Then retract the plunger so that the lower
purity grade (HP) used as the carrier gas. (Warning—These liquid meniscus falls on the 5 µL mark, and record the volume
gases are normally stored in cylinders under high pressure. of liquid in the syringe. After the sample has been injected,
These gases also dilute the oxygen content of the surrounding again retract the plunger so that the lower liquid meniscus falls
air when they leak.) on the 5 µL mark, and record the volume of liquid in the
19.3 Cell Electrolyte Solution, 70 % acetic acid, combine syringe. The difference in the two volume readings is the
300 mL reagent water (see 6.2) with 700 mL acetic acid (see volume of sample injected.
19.1) and mix well. 21.2 Alternately, obtain the sample injection device mass
19.4 Chloride, Standard Stock Solution, 1000 mg chloride before and after injection to determine the amount of sample
per litre. Accurately dispense 1.587 g of chlorobenzene into a injected. This method provides greater precision than the
500 mL volumetric flask and dilute to volume with 2,2,4, volume delivery method, provided a balance with a precision
trimethyl pentane (isooctane). of 60.01 mg is used and the syringe is carefully handled to
obtain repeatable weighings.
NOTE 2—The exact concentration of chloride may be determined by
multiplying the mass of chlorobenzene by the product of the atomic mass 21.3 Inject the sample into the pyrolysis tube at a rate not to
of chlorine divided by the molecular mass of chlorobenzene and then exceed 0.5 µL ⁄s.
multiplying that result by 2000.
21.4 Below 5 µg ⁄g, the needle-septum blank will become
w 3 m 1 3 2000 increasingly more obvious. To improve precision, insert the
Cl ~ mg/ L ! 5 (6)
m2 syringe needle into the hot inlet and then wait until the
where: needle-septum blank is titrated before injecting the sample or
standard.
w = mass of chlorobenzene weighed,
m1 = atomic mass of chlorine, and 21.5 For specimens containing more than 25 µg ⁄g Cl only
m2 = molecular mass of chlorobenzene. 5.0 µL of sample need be injected.
19.5 Chlorine, Standard Solution, 10 mg chloride per litre. 21.6 Verify the system recovery, the fraction of chlorine in
Pipet 1.0 mL of chloride stock solution (see 19.4) into a the standard that is titrated, every 4 h by using the standard
100 mL volumetric flask and dilute to volume with 2,2,4, solution (see 19.5). System recovery is typically 85 % or better.
trimethyl pentane (isooctane). 21.7 Repeat the measurement of the calibration standard at
19.6 Chlorobenzene, reagent grade. least three times.
19.7 Gas Regulators, two-stage gas regulator must be used 21.8 Check the system blank daily with reagent grade
on the reactant and carrier gas. isooctane (see 19.8). Subtract the system blank from both
sample and standard data. The system blank is typically less
19.8 Isooctane, 2,2,4-trimethylpentane, reagent grade.
than 0.2 µg ⁄g chloride once the needle-septum blank has been
19.9 Oxygen, high purity grade, used as the reactant gas. titrated (see 21.4).
--````,`,,,,,,`,`,``,,`,,,,,``-`-`,,`,,`,`,,`---

D4929 − 19
22. Calculation the values for its type described in Section 32. (Warning—
22.1 Calculate chloride concentration in the naphtha frac- Exposure to excessive quantities of high energy radiation such
tion as follows: as those produced by X-ray spectrometers is injurious to
health. The operator needs to take appropriate actions to avoid
22.1.1 For microcoulometers, which read directly in nano-
exposing any part of their body, not only to primary X-rays, but
grams of chloride, the following equations apply:
also to secondary or scattered radiation that might be present.
Sample Readout Blank Readout The X-ray spectrometer should be operated in accordance with
Chloride, µg/g 5 2 (7)
~ V ! ~ D ! ~ RF! ~ V ! ~ D ! ~ RF! the regulations governing the use of ionizing radiation.)
or 23.2 Monochromatic Wavelength Dispersive X-ray Fluores-
Sample Readout Blank Readout cence (MWDXRF) Spectrometer, equipped for X-ray detection
Chloride, µg/g 5 2 (8) at 0.473 nm (4.73 A) which also includes the following:
~ M ! ~ RF! ~ M ! ~ RF!
23.2.1 X-ray Source, capable of producing X-rays to excite
where: chlorine. X-ray tubes with a power of >20 W capable of
Readout = displayed integrated value (sample/standard/ producing Pd Lα, Ag Lα, Ti Kα, Sc Kα, or Cr Kα radiation are
blank), recommended for this purpose.
V = volume injected µL, 23.2.2 Optical Path, designed to minimize the absorption
D = density, g/mL (11.3), along the path of the excitation and fluorescent beams using a
RF = recovery factor, ration of chloride determined in vacuum or a helium (see 24.6) atmosphere. If vacuum is used,
standard divided by known standard content mi- a level of lower than 2.7 kPa (<20 Torr) is recommended. The
nus the system blank. calibration and test measurements must be done with identical
Standard Readout Blank Readout optical paths, including vacuum or helium pressure.
RF 5 2
~ V ! ~ D ! ~ C s! ~ V ! ~ D ! ~ C s! 23.2.3 Incident-beam Monochromator, capable of focusing
and selecting a single wavelength of characteristic X-rays from
M = mass of sample specimen, mg, and the source onto the specimen.
Cs = concentration of standard, mg/L
23.2.4 Fixed-channel Monochromator, suitable for dispers-
22.1.2 For microcoulometers with only analog signal output ing chlorine Kα X-rays.
to a recorder the following equation applies: 23.2.5 Detector, designed for efficient detection of chlorine
~ A ! ~ X ! ~ 0.367! Kα X-rays.
Chloride, µg/g 5 2B (9) 23.2.6 Single-channel Analyzer, an energy discriminator to
~ R ! ~ Y ! ~ M ! ~ RF!
monitor only chlorine radiation.
where:
A = area in appropriate units, 23.3 Monochromatic Energy Dispersive X-ray Fluorescence
X = recorder sensitivity for full-scale response, mV, (MEDXRF) Spectrometer, including the following:
0.367 = 23.3.1 Source of X-ray Excitation, X-ray tube with Ag or Pd
~ 35.45 gCl/eq! ~ 1023 V/mV! ~ 106 µg/g !
anode, in combination with HOPG Bragg monochromating
~ 96 500 coulombs/eq!
X-ray optics. The monochromator must produce monochro-
R = resistance, Ω, matic Ag or Pd L radiation. Other anode materials and
Y = area equivalence for a full-scale response on the monochromators may be utilized, however stated precision and
recorder per second-area units per second, bias may not apply.
M = mass of sample, g, 23.3.2 Optical Path, the system must allow flushing of the
RF = recovery factor, and optical path with helium (see 24.6). Alternatively, a vacuum of
B = system blank, µg/g Cl. ≤4.0 kPa (≤30.4 Torr) can be applied to the optical path. When
22.2 The concentration of organic chloride in the original the air in the optical path is relatively small, then vacuum or
crude oil sample specimen can be obtained by multiplying the helium may be optional. Follow manufacturer’s recommenda-
chloride concentration in the naphtha fraction (see 22.1) by the tions.
naphtha fraction (see 12.1). 23.3.3 X-ray Detector, with a resolution value not to exceed
175 eV at 5.9 keV (10 000 cps). A Si drift chamber detector
PROCEDURE C—X-RAY FLUORESCENCE (SDD) has been found suitable for use. Using a detection
SPECTROMETRY system with this minimum spectral resolution has been shown
to eliminate the potential effect of spectral interference from
23. Apparatus sulfur or other elements in the naphtha sample.
23.1 Any spectrometer of the following type: Monochro- 23.3.4 Signal Conditioning and Data Handling Electronics,
matic Wavelength Dispersive X-ray Fluorescence (MWDXRF) including the functions of X-ray intensity counting, spectra
Spectrometer, Monochromatic Energy Dispersive X-ray Fluo- handling by background subtraction and deconvolution, calcu-
rescence (MEDXRF) Spectrometer, or Energy Dispersive X-ray lation of overlap corrections and conversion of chlorine X-ray
Fluorescence (EDXRF) Spectrometer can be used if it includes intensity into mg/kg chlorine concentration.
the following features for its type described in this section and 23.4 Energy Dispersive X-ray Fluorescence (EDXRF)
the precision and bias of the test results are in accordance with Spectrometer, required design features include:
--````,`,,,,,,`,`,``,,`,,,,,``-`-`,,`,,`,`,,`---

D4929 − 19
23.4.1 Source of X-ray Excitation, X{ray tube with excita- 24.3 Chlorine Dopant (CD), a high{purity standard with a
tion energy above 2.9 keV. certified chlorine content. Trichloroethylene and 1,2,4-
23.4.2 X-ray Detector, with high sensitivity and a resolution trichlorobenzene have been found to be acceptable chlorine
value (Full Width at Half Maximum, FWHM) not to exceed dopants. Use the certified chlorine concentration when calcu-
175 eV at 5.9 keV (10 000 cps). A Si drift chamber detector lating the exact concentrations of chlorine in calibration
(SDD) has been found suitable for use. standards. (Warning—Breathing trichloroethylene vapors may
23.4.3 Filters, or other means of discriminating between cause drowsiness and dizziness. Causes eye and skin irritation.
chlorine Kα radiation and other X-rays of different energy. The Aspiration hazard if swallowed. Can enter lungs and cause
other means include software solutions. damage. May cause cancer based on animal studies. May cause
23.4.4 Optical Path, the system must allow flushing of the liver damage.) (Warning—1,2,4-trichlorobenzene may cause
optical path with helium (see 24.6). Alternatively, a vacuum of respiratory tract irritation. Harmful if swallowed. Causes eye
≤4.0 kPa (≤30.4 Torr) can be applied to the optical path. and skin irritation.)
23.4.5 Signal Conditioning and Data Handling Electronics, 24.4 Counting Gas, for instruments equipped with flow
that include the functions of X-ray intensity counting, a proportional counters. The purity of the counting gas should be
minimum of two energy regions, spectral overlap corrections, in agreement with the specification provided by the instrument
background corrections, and conversion of chlorine X-ray manufacturer.
intensity into mass percent chlorine concentration.
24.5 Drift Correction Monitor(s) (Optional)—Several dif-
23.5 Additionally, the following apparatus is needed when
ferent materials have been found to be suitable for use as drift
using all x{ray spectrometers within the scope of this method:
correction monitors. Appropriate drift monitor samples should
23.5.1 Display or Printer, that reads out in mg/kg chlorine.
be permanent materials that are stable with respect to repeated
23.5.2 Removable Sample Cell, an open{ended specimen
exposure to X-rays. Stable liquids, glass or metallic specimens
holder compatible with the sample and the geometry of the
are recommended. Liquids, pressed powders, and solid mate-
XRF spectrometer. A disposable cell is recommended. The
rials that degrade with repeated exposure to X-rays should not
sample cell should not leak when fitted with X-ray transparent
be used. Examples of chlorine containing materials that have
film (see 23.5.3).
been found to be suitable include a renewable liquid petroleum
23.5.3 X-ray Transparent Film, for containing and support-
material, a metal alloy, or a fused glass disk. The monitor’s
ing the test specimen in the sample cell (see 23.5.2) while
counting rate, in combination with count time, shall be
providing a low{absorption window for X-rays to pass to and
sufficient to give a relative counting error of less than 1 %. The
from the sample. Any film resistant to chemical attack by the
counting rate for the monitor sample is determined during
sample, free of chlorine, and X-ray transparent can be used, for
calibration (see 27.4) and again at the time of analysis (see
example, polyester, polypropylene, polycarbonate, and poly-
28.1). These counting rates are used to calculate a drift
imide. However, samples of high aromatic content can dissolve
correction factor (see 29.1).
polyester and polycarbonate films.
23.5.4 Analytical Balance, for preparing calibration NOTE 3—Calibration standards may be used as drift{monitor samples.
standards, capable of weighing to the nearest 0.1 mg and up to Because it is desirable to discard test specimens after each determination,
a lower cost material is suggested for daily use. Any stable material can be
100 g.
used for daily monitoring of drift.
NOTE 4—The effect of drift correction on the precision and bias of this
24. Reagents and Materials test method has not been studied.
24.1 Purity of Reagents—Reagent grade chemicals shall be 24.5.1 Drift correction is usually implemented automati-
used in all tests. Unless otherwise indicated, it is intended that cally in software, although the calculation can readily be done
all reagents conform to the specifications of the Committee on manually. For X-ray instruments that are highly stable, the
Analytical Reagents of the American Chemical Society where magnitude of the drift correction factor may not differ signifi-
such specifications are available.7 Other grades may be used, cantly from unity.
provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of 24.6 Helium Gas, for instruments equipped with a helium
the determination. optical path (optional for some analyzers). The minimum
purity 99.9 %. If helium is used, it is recommended to limit
24.2 Calibration Check Samples, portions of one or more variations in pressure and temperature to within 10 % relative.
liquid petroleum or product standards of known or certified When connecting a new helium gas cylinder, always run a
chlorine content and not used in the generation of the calibra- blank measurement to ensure the helium gas line is purged of
tion curve. The check samples shall be used to determine the air.
precision and accuracy of the initial calibration (see 27.6).
24.7 Quality Control Samples, stable petroleum or product
samples or solids representative of the samples of interest that
7
Reagent Chemicals, American Chemical Society Specifications, American are run on a regular basis to verify that the system is in
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not statistical control (see Section 31).
listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia NOTE 5—Verification of system control through the use of QC samples
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, and control charting is highly recommended. It is recognized that QC
MD. procedures are the province of the individual laboratory.
--````,`,,,,,,`,`,``,,`,,,,,``-`-`,,`,,`,`,,`---

D4929 − 19
NOTE 6—Suitable QC samples can often be prepared by combining 25.7 If the instrument (see Section 23) is equipped with a
retains of typical samples if they are stable. QC samples must be stable replaceable secondary (also called safety) window, it should be
over long periods.
checked periodically and changed if it is wrinkled, ripped,
24.8 White Mineral Oil (WMO), ACS Reagent Grade con- dirty, or contaminated by a leaking sample cup. When chang-
taining less than 1 mg/kg chlorine or other suitable base ing the window, follow the precautions given in 25.2 and 25.3.
material containing less than 1 mg ⁄kg chlorine. The chlorine
25.8 See Practice D7343 for more detailed sample handling
content, if any, of the base material needs to be included in the
and preparation information.
calculation of calibration standard concentration (see 27.1).
When the chlorine content of the solvent or reagent is not
certified, verify the absence of chlorine. Use the purest grades 26. Preparation of Apparatus
for the preparation of calibration standards. It is also important 26.1 Ensure that the XRF analyzer has been installed and
to measure and correct for the C/H ratio (see Section 29.7), if put into operation according to manufacturer’s instructions.
--````,`,,,,,,`,`,``,,`,,,,,``-`-`,,`,,`,`,,`---
it differs significantly from the calibration standards when Allow sufficient time for instrument electronics to stabilize.
calculating the final results. Perform any instrument checkout procedures required. When
possible, the instrument should be run continuously to maintain
25. Sampling and Specimen Preparation optimum stability.
25.1 Samples shall be taken in accordance with the instruc- 26.1.1 Use the count time (T) recommended by the instru-
tions in Practices D4057 or D4177 when applicable. ment manufacturer for the lowest chlorine concentration ex-
pected.
25.2 When reusable sample cells are used, clean and dry
cells before each use. Disposable sample cells shall not be 27. Calibration
reused. For each sample, an unused piece of X-ray film is
required for the sample cell. Avoid touching the inside of the 27.1 Prepare a set of calibration standards bracketing the
sample cell, the portion of the window film in the cell, or the expected concentration range in the samples by careful mass
instrument window (if the instrument is so equipped) that is dilution of a chlorine dopant (CD, see 24.3) with a chlorine{
exposed to X-rays. Oil from fingerprints can affect the reading free white mineral oil (WMO, see 24.8) or other suitable base
when analyzing for low levels of chlorine. Wrinkles in the film material. Trichloroethylene and 1,2,4-trichlorobenzene have
will affect the intensity of the chlorine X-rays transmitted. been found to be suitable chlorine dopants (see 24.3). The
Therefore, it is essential that the film be taut and clean to concentrations of the unknown samples must lie within the
ensure reliable results. calibration range that is used. All standards used in the analysis
must be from a reliable and consistent source, which can
25.3 Use the appropriate film for the sample type. Samples include commercially available standards. Recommended
of high aromatic content may dissolve polyester, polypropyl- nominal chlorine concentration standards are listed as follows
ene and polycarbonate films. In these cases, other materials for the scope of this test method: 0 mg ⁄kg (base material),
besides these films may be used for X-ray windows, provided 5 mg ⁄kg, 10 mg ⁄kg, 25 mg ⁄kg, 50 mg ⁄kg, and 100 mg ⁄kg.
that they do not contain any elemental impurities. Follow
instrument manufacturer’s recommendations where possible. NOTE 7—It is recommended to calibrate the XRF analyzer higher than
the expected organic chloride concentration in the crude oil, because
25.4 Because impurities and thickness variations can occur distillation of the crude oil will concentrate organic chlorides in the
in commercially available transparent films and vary from lot naphtha fraction. Use the amount of naphtha collected (Eq 3) to optimize
the calibration curve. For example, if the naphtha fraction is 0.5, the
to lot, use calibration-check samples (see 24.2) to verify
measured concentration of chloride in the naphtha fraction can be
calibration integrity after starting each new batch of film. The expected to be twice the amount of the crude.
analyzer may need recalibration if the type or thickness of the
window film is changed. 27.1.1 Take into account any chlorine in the base materials
when calculating the chlorine content (mg/kg) in each of the
25.5 Place the sample in the cell using techniques consistent calibration standards as shown in Eq. 10:
with good practice for the particular instrument being used.
Cl 5 @ ~ CD 3 Cl CD ! 1 ~ WMO 3 Cl WMO ! # □⁄□ ~ CD 1 WMO!
Although chlorine radiation will emerge from only a small
distance into the sample, scatter from the sample cell and the (10)
sample can vary. Laboratory personnel shall ensure that the where:
sample cell is filled above a minimum depth, beyond which Cl = mass fraction of the chlorine of the prepared
additional sample does not significantly affect the count rate. standards, mg/kg,
Generally, fill the sample cell to a minimum of one-half of the CD = actual mass of the chlorine dopant, g,
cell’s capacity. After the sample cell is filled and film is ClCD = the mass fraction of chlorine in the chlorine
attached, provide a vent above the sample to prevent bowing of dopant, mg/kg, typically 0.8095 mg ⁄kg for trichlo-
the film by accumulating vapors. roethylene and 0.861 mg ⁄kg for 1,2,4-
25.6 Ensure the sample is not leaking after preparation, and trichlorobenzene,
perform the analysis of the specimen promptly after preparing WMO = actual mass of white mineral oil, g, and
ClWMO = mass fraction of chlorine in the white mineral oil,
the specimen. Do not let the specimen remain in the sample
mg/kg.
cell any longer than necessary before collecting the data.

D4929 − 19
27.1.2 Alternatively, commercially available standards can 28.2 Analyze each sample of interest as follows:
be used provided their chlorine concentrations are accurately
28.3 Prepare a test specimen of the sample of interest
known and they approximate the nominal recommended con-
according to Section 25. Quality control samples shall be
centrations listed in 27.1.
prepared and run identically to any unknown sample.
27.1.3 Store all standards and QC samples in glass bottles in
a cool, dark place until required. The glass bottles shall either 28.4 Place the sample cell containing the test specimen in
be dark or wrapped in opaque material, and closed with glass the X{ray beam, as directed in the instrument manufacturer’s
stoppers, inert plastic lined screw caps, or impermeable enclo- instructions. Allow the X{ray optical path to come to equilib-
sures. As soon as any sediment or change of concentration is rium.
observed, discard the sample.
28.5 Determine the net chlorine intensity for MWDXRF
27.2 Establish calibration curve data by carefully determin- spectrometers by measuring the total counts of chlorine
ing the net intensity of the emitted chlorine radiation from each fluorescence, and then dividing the total counts by the mea-
of the standards by the procedures described in Sections 28 and surement time in seconds to calculate I (see Eq 11). Calculate
29. the concentration of chlorine in the test specimen as instructed
27.3 Construct a calibration model by using the software in Section 29.
and algorithms supplied by the equipment vendor. The calibra- 28.5.1 If the sulfur concentration of the sample is
tion model typically takes one of the following linear forms ≥0.5 mass %, it is recommended to sulfur correct the chlorine
(refer to the equipment vendor’s software documentation to measurement results. This correction is performed automati-
determine the exact form): cally by the analyzer software either by manual input of the
I 5 Cl*m1b (11) sulfur concentration or direct sulfur measurement of the
sample. Refer to equipment vendor’s software documentation
Cl 5 l*m1b (12) to determine the exact form of the correction.
--````,`,,,,,,`,`,``,,`,,,,,``-`-`,,`,,`,`,,`---
where: 28.6 For MEDXRF spectrometers, determine the peak area

l = net intensity for the chlorine radiation, of the chlorine Kα radiation at 2.622 keV. The net count{rate
Cl = chlorine concentration in mg/kg, will be calculated by subtracting the background. The back-
m = slope, and ground spectrum, measured with a chlorine{free white oil or
b = intercept. other matrix matching blank sample (see 24.8) is adapted to the
27.4 When using drift correction monitors, determine the measured spectrum using adjustment regions (see Note 8)
intensity of the drift correction monitor sample(s) during the following the instrument manufacturer’s instructions and then
calibration procedure. The value determined corresponds to the subtracted from the measured spectrum. Determine the cor-
factor A in Eq 13 in 29.1. rected counting rate and calculate the concentration of the
27.5 A sulfur calibration model may be required for spec- sample as described in Section 29.
trometers utilizing a direct sulfur measurement in the sulfur NOTE 8—Background adjustment regions of 2.8 keV to 3.3 keV are
correction factor. If required, construct a calibration model by suitable when using an Ag target X-ray tube. When using a Pd target X-ray
using the software and algorithms supplied by the equipment tube, a region of about 2.7 keV to 3.2 keV can be used. Ensure that the
vendor. The calibration model may be empirical or make use of region used is free from chlorine overlap.
fundamental parameters (refer to the equipment vendor’s 28.6.1 Sulfur Correction MEDXRF—This correction is per-
software documentation to determine the exact form). formed automatically by the analyzer software either by
27.6 Immediately after completing the calibration, deter- manual input of the sulfur concentration or direct sulfur
mine the chlorine concentration of one or more of the calibra- measurement of the sample. Refer to equipment vendor’s
tion check samples (24.2). The determined value shall be in the software documentation to determine the exact form of the
range defined by the certified concentration plus or minus the correction.
repeatability of this test method. When this is not the case, the 28.7 For EDXRF spectrometers, the chlorine concentration
calibration process and calibration standards are suspect and is automatically calculated from the calibration, using the
corrective measures should be taken. The degree of matrix instrument software.
mismatch between samples and standards should also be
28.7.1 Sulfur Correction EDXRF—This correction is per-
considered when evaluating a calibration. Statistical quality
formed automatically by the analyzer software either by
control charts may be prepared for these materials to establish
manual input of the sulfur concentration or direct sulfur
if the method is in statistical control, as described in Section
measurement of the sample. Refer to equipment vendor’s
31.
software documentation to determine the exact form of the
28. Procedure correction.
28.1 When using drift correction monitors, before analyzing 28.8 If the measured intensity for a test specimen is greater
samples on a given day, analyze the drift correction monitor(s) than the highest count rate in the calibration curve, quantita-
and determine the counting rate, using the same material as tively dilute a fresh portion of the sample with the base
used at the time of calibration. The value determined corre- material used to prepare the calibration standards. Dilute the
sponds to the factor B in 29.1. sample so the resultant count rate is within the limits of the

10
Licensee=Kurdistan Pipeline Company/8246336001, User=Saadi, Gharbi
D4929 − 19
calibration curve. Repeat the procedures described in 28.2-28.7 Cl o 5 @ Cl d 3 ~ M o 1 M b ! □⁄□M o # 2 @ Cl b 3 ~ M b ⁄ M o ! # (15)
on a test specimen of the diluted sample.
where:
29. Calculations Cld = concentration of chlorine in test specimen of the
diluted sample (from 28.8), mg/kg,
29.1 When using a drift monitor sample (optional), calcu- Mo = mass of original sample, g,
late a drift correction factor (F) for changes in daily instrument Mb = mass of base material used to dilute sample, g, and
sensitivity according to Eq 13. If a drift monitor is not used, F Clb = concentration of chlorine in diluent, mg/kg.
is set equal to 1.
29.7 The carbon/hydrogen (C/H) ratio correction formula,
F 5 A⁄B (13) which is applicable when the base material used for the
where: calibration standards is white oil, is shown in Eq 16:
F = drift correction factor, Cl C⁄H 5 $ @ 1.195 2 0.0164 ~ C ⁄ H ! whiteoil # □⁄□ @ 1.195
A = counting rate of the drift correction monitor as deter- 2 0.0164 ~ C ⁄ H ! # % 3 Cl whiteoil (16)
mined at the time of the calibration (see 27.4), and
B = counting rate of the drift correction monitor as deter- where:
mined at the time of analysis. ClC/H = chlorine concentration corrected for C/H ratio
matrix differences,
29.2 For MWDXRF spectrometers, calculate the drift{ (C/H)whiteoil = mass ratio of carbon to hydrogen for white
corrected count rate, or intensity, (Icor) for the test specimen as oil, typically 5.7,
follows: (C/H) = mass ratio of carbon to hydrogen for the
I cor 5 F*I (14) sample, and
Clwhiteoil = chlorine concentration as derived from the
where: calibration graph.
F = drift correction factor, calculated in Eq 13, and
I = net count rate (or intensity) for test specimen. 29.7.1 The value for C/H mass ratio is input for each
unknown sample. The Clwhiteoil will be corrected for the
29.2.1 Calculate the chlorine content (Cl) of the test speci- different C/H ratios. Accordingly, if standards are prepared
men by using the drift{corrected count rate (Icor) in place of I with a different solvent, the C/H ratio for that solvent should be
in Eq 11 of 27.3. In many cases the instrument vendor will used in place of (C/H)whiteoil. Differences between the C/H ratio
provide software or the required calculations. The use of the between standards and samples will contribute to error in the
factor F to correct the counting rate of chlorine is optional. measured result. It is the analyst’s discretion as to when this
29.3 For MEDXRF spectrometers, the net counting rate, or error is large enough to be corrected by Eq 16. If unsure
intensity, is given by the spectral deconvolution of the chlorine whether or not to apply correction, follow the analyzer manu-
Kα line after subtracting the background spectrum. facturer’s instructions.
--````,`,,,,,,`,`,``,,`,,,,,``-`-`,,`,,`,`,,`---
29.3.1 The use of the factor F to correct the counting rate of 29.8 The concentration of the organic chloride in the origi-
chlorine is optional. nal crude oil sample specimen can be obtained by multiplying
29.3.2 Calculate the chlorine content (Cl) of the sample by the chlorine concentration in the naphtha fraction, Cl in Eq 11
inserting the corrected net counting rate in the calibration Eq and Eq 12 (see 27.3), by the naphtha fraction, f, in Eq 3 (see
12 from 27.3. In many cases the instrument vendor will provide 12.1).
software for the required calculations.
29.4 For EDXRF spectrometers, the concentration of chlo- 30. Report
rine in the sample is automatically calculated from the calibra- 30.1 Report the organic chloride content of the original
tion curve. crude oil sample specimen in µg/g (or mg/kg) as calculated in
29.5 If the specimens have ≥0.5 mass % sulfur, then it is accordance with 17.2 for Procedure A, 22.2 for Procedure B,
recommended that matrix corrections for sulfur be made. In and/or 29.8 for Procedure C.
some systems, the sulfur lines might be interfering with the 30.1.1 The organic chloride content of the naphtha fraction
intensity of chlorine. In that case, line overlap corrections is also expressed as µg/g (or mg/kg) and is calculated in Eq 5
might be required. Manufacturer’s software typically provides for Procedure A, Eq 7-9 for Procedure B, and/or Section 29 for
a method to correct for matrix effects and interferences. In Procedure C. These results are used to calculate the organic
some instances, both matrix correction and correction for chloride content of the original crude oil sample specimen in
interference may be required. In other specimens only one of 30.1.
these corrections must be applied, and in other specimens still 30.2 Indicate that the organic chloride in crude oil results
no correction at all is required. Follow manufacturer recom- were determined by Test Method D4929, Procedure A; Test
mendations for applying sulfur correction. Method D4929, Procedure B; or Test Method D4929, Proce-
29.6 If the test specimen was prepared from a quantitatively dure C. For Procedure C, also report whether the result was
diluted sample, correct the measured concentration for sample obtained by MWDXRF, MEDXRF, or EDXRF. Denote if
dilution. The chlorine concentration (Clo) in the original, method modifications, such as described in Appendix X2, were
undiluted sample is calculated as follows: used during the analysis.

D4929 − 19
31. Quality Assurance/Quality Control (QA/QC) obvious signs of damage to the sample such as leaking sample
31.1 Confirm the performance of the instrument and the test cells, crinkled sample cell window and inspection of any
procedure by analyzing a QC sample. secondary film.
31.1.1 When QA/QC protocols are already established in 31.3.4 Observation of the Resultant Analysis—If a result is
the testing facility, these may be used when they confirm the considered outside normal thresholds, a repeat of the analysis
reliability of test result. should be carried out to confirm anomalous results.
31.1.2 When there is no QA/QC protocol established in the 31.3.5 Regular checks should be carried out to ensure that
testing facility, Appendix X1 may be used as the QA/QC purging gas performance is within the instrument manufac-
system. ture’s specification.
31.3.6 Quality control standards shall be run on a regular
31.2 Users of this test method are advised that in contractual basis. If drift monitors are used, they shall also be run on a
agreements, one or more of the contracting parties can and may regular basis. The tolerance levels of the checks made using
make Appendix X1 mandatory practice. these monitors should be such that a protocol of either drift
31.3 Additionally, the following QA/QC steps should be correction or total recalibration is carried out if the results fall
observed when using Procedure C: outside these levels. All measurements should be repeated
31.3.1 In addition to running a quality control sample between the last accepted monitor result and point of non{
(24.7), it is strongly recommended that the calibration blank be compliance should a current monitor measurement prove to be
analyzed on a daily basis. outside acceptable levels.
31.3.1.1 The measured concentration for the blank should
be less than 1 mg ⁄kg chlorine. If the measured concentration 32. Precision and Bias8
for the blank is greater than 1 mg ⁄kg, repeat the measurement 32.1 Precision—The precision of these procedures as deter-
of the blank (use a fresh sample and fresh cell). If the measured mined by the statistical examination of the interlaboratory test
concentration of the blank is still greater than 1 mg ⁄kg, results is provided below. The precision statements were
restandardize the instrument and repeat the measurement of the determined on samples analyzed by Procedures A, B, and C as
blank (use a fresh sample and fresh cell). If the result falls written. When method modification is employed, such as that
outside the acceptable range, carry out a full calibration. If the described in Appendix X2, the published precision may not
sample loading port becomes contaminated, especially when
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apply.
analyzing <20 mg ⁄kg chlorine level samples, it is necessary to
32.1.1 Repeatability—The difference between successive
open and clean it according to manufacturer’s recommenda-
results obtained by the same operator with the same apparatus
tions before further use.
under constant operating conditions on identical test materials
31.3.2 It should be noted that in order to obtain a good fit for
would, in the long run, in the normal and correct operation,
the calibration at low concentrations, it may be necessary to
exceed the following values only in one case in twenty.
change the weighting factor in the regression. It may also be
32.1.1.1 Procedure A—Values can be obtained for
beneficial to change the weighting method used. Many soft-
organically-bound chlorine for any given concentration above
ware packages default to square root error weighting but have
1 µg ⁄g Cl (in the original crude oil specimen) as follows:
the possibility of using linear error weighting or no error
weighting. r 5 0.32 ~ X10.33! 0.644 (17)
31.3.3 Results Validation—Once a standard or sample has where:
been measured, a procedure should be carried out to validate
X = µg/g chloride.
that measurement. This requires the operator to check for
See Table 2 for calculated values. See Note 9 for details of
the ILS.
32.1.1.2 Procedure B—Values can be obtained for
1 µg ⁄g Cl (in the original crude oil specimen) as follows:
r 5 1.01 ~ X 2 0.17! 0.467 (18)
where:
X = µg/g chloride.
the ILS.
32.1.1.3 Procedure C—Values can be obtained for
8
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1293 for Procedures A and B,
and RR:D02-1875 for Procedure C. Contact ASTM Customer Service at
FIG. 1 Recovery of Organic Chloride Spikes service@astm.org.

12
D4929 − 19
TABLE 1 Precision Equations, Procedure C XRF TABLE 3 Calculated Reproducibility R Values, All Procedures
A
Repeatability r, mg/kg Procedure Procedure Procedure C
MWDXRF Cl, mg/kg A B R, mg/kgC
r 5 0.643*X 0.44 (19)
R, µg/gA R, µg/gB MWDXRF MEDXRF EDXRF
MEDXRF 0.44 1 0.8 1.2 1.2 1.5 2.4
r 5 0.591*X (20)
2 1.2 1.8 1.7 2.0 3.0
3 1.5 2.1 2.0 2.4 3.6
EDXRF 4 1.8 2.5 2.3 2.8 4.1
r 5 0.934s X 1 0.4d 0.48 (21)
5 2.1 2.8 2.5 3.0 4.5
Reproducibility R, mg/kgA 6 2.3 3.0 2.7 3.3 4.9
MWDXRF 8 2.7 3.5 3.1 3.7 5.6
R 5 1.235*X 0.44 (22) 10 3.1 3.8 3.4 4.1 6.2
12 3.5 4.2 3.7 4.5 6.7
MEDXRF A
R 5 1.500*X 0.44 (23) Values calculated from Eq 25.
B
Values calculated from Eq 26.
C
EDXRFB Values calculated from Eq 22 for MWDXRF, Eq 23 for MEDXRF, and Eq 24 for
R 5 2.000s X 1 0.4d 0.48 (24) EDXRF.
A
Where X = mg/kg chloride
B
The degrees of freedom associated with the reproducibility estimate from this
round robin study are 29. Since the minimum requirement of 30 (in accordance
with Practice D6300) is not met, users are cautioned that the actual reproducibility
may be significantly different than these estimates.
where:
X = µg/g chloride.
TABLE 2 Calculated Repeatability r Values, All Procedures
the ILS.
Procedure Procedure Procedure C 32.1.2.3 Procedure C—Values can be obtained for
Cl, mg/kg A B r, mg/kgC
r, µg/gA r, µg/gB MWDXRF MEDXRF EDXRF
1 mg ⁄kg Cl (in the original crude oil specimen) as specified in
1 0.4 0.9 0.6 0.6 1.1
2 0.6 1.3 0.9 0.8 1.4 Table 1. See Table 3 for calculated values. See Note 10 for
3 0.7 1.6 1.0 1.0 1.7 details of the ILS.
4 0.8 1.9 1.2 1.1 1.9 32.1.3 Procedure C—Between{Method Relative Bias can be
5 0.9 2.1 1.3 1.2 2.1
6 1.1 2.3 1.4 1.3 2.3 expressed as follows:
8 1.3 2.6 1.6 1.5 2.6 32.1.3.1 Degree of Agreement between results by MEDXRF
10 1.4 2.9 1.8 1.6 2.9 and MWDXRF—Results on the same materials produced by
12 1.6 3.2 1.9 1.8 3.1
A
MEDXRF and MWDXRF have been assessed in accordance
B
with procedures outlined in Practice D6708. The findings are
C
Values calculated from Eq 19 for MWDXRF, Eq 20 for MEDXRF, and Eq 21 for that the degree of agreement between results from MEDXRF
EDXRF. and MWDXRF, can be further improved by applying Eq 27
listed in Table 4. No sample{specific bias, as defined in Practice
D6708, was observed after the bias{correction for the materials
in the scope of this method.
1 mg ⁄kg Cl (in the original crude oil specimen) as specified in 32.1.3.2 Degree of Agreement between results by EDXRF
Table 1. See Table 2 for calculated values. See Note 10 for and MEDXRF—Results on the same materials produced by
details of the ILS. MEDXRF and MWDXRF have been assessed in accordance
32.1.2 Reproducibility—The difference between two single with procedures outlined in Practice D6708. The findings are
and independent results obtained by different operators work- that the degree of agreement between results from EDXRF and
ing in different laboratories on identical material would, in the MEDXRF, can be further improved by applying Eq 28 listed in
long run, exceed the following values only in one case in Table 4. No sample{specific bias, as defined in Practice D6708,
twenty. was observed after the bias{correction for the materials in the
32.1.2.1 Procedure A—Values can be obtained for scope of this method.
1 µg ⁄g Cl (in the original crude oil specimen) as follows: TABLE 4 Procedure C Between-Method Bias Outcome
R 5 0.7 ~ X10.33! 0.644 (25) Method X Method Y Suggested Bias
CorrectionA
where: MEDXRF MWDXRF
Ŷ 5 X 2 0.658 (27)
X = µg/g chloride.
See Table 3 for calculated values. See Note 9 for details of EDXRF MEDXRF
Ŷ 5 X 2 0.519 (28)
the ILS.
32.1.2.2 Procedure B—Values can be obtained for EDXRF MWDXRF No bias correction
organically-bound chlorine for any given concentration above A
Where:
1 µg ⁄g Cl (in the original crude oil specimen) as follows: Ŷ = predicted Y-method value
X = single X-method measured results
R 5 1.32 ~ X 2 0.17! 0.467 (26)
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13
D4929 − 19
32.1.3.3 Degree of Agreement between results by EDXRF by technology was eight MWDXRF analyzers, nine MEDXRF analyzers,
and MWDXRF—Results on the same materials produced by and six EDXRF analyzers. Practice D6300 was followed for the analysis
of data. The data would not support a pooled precision statement, so
EDXRF and MWDXRF have been assessed in accordance with separate precisions were determined for each XRF technique. See
procedures outlined in Practice D6708. The findings are that no RR:D02-1875 for details of this study.
bias{correction considered in Practice D6708 can further im-
32.2 Bias—The bias for either Procedure A or B has been
prove the agreement between results from EDXRF and
demonstrated by performing analyses using known spiked
MWDXRF for the materials studied. No sample{specific bias,
concentrations of various organic chloride compounds in a
as defined in Practice D6708, was observed for the materials in
variety of crude oils to be lower than the true value. This is
the scope of this method.
because not all of the volatile components will distill from a
NOTE 9—Procedures A and B Interlaboratory Study—Ten crude complex crude oil under the conditions of this test method. The
samples were prepared from four crudes. Ten laboratories reported the extent of this bias is shown in Fig. 1, where various recoveries
distillation data. Eight laboratories reported data for Procedure A and six
laboratories reported data for Procedure B. One laboratory’s data was are shown plotted against the known concentration of pure
removed from the statistics for Procedure A. Separate precision statements organic-chloride compound spikes.
were determined for each procedure. See RR:D02-1293 for details of this 32.2.1 See Fig. 2 for a recovery plot of Procedure C.
study.
NOTE 10—Procedure C Interlaboratory Study—Eight participants dis- 33. Keywords
tilled ten crude samples in blind duplicate and performed washes on the
twenty naphtha fractions. Six of the eight participants measured each 33.1 chlorine; coulometry; crude oil; EDXRF; Energy Dis-
washed naphtha fraction by monochromatic wavelength dispersive XRF persive X-ray Fluorescence; MEDXRF; Monochromatic En-
(MWDXRF), monochromatic energy dispersive XRF (MEDXRF), and ergy Dispersive X-ray Fluorescence; Monochromatic Wave-
energy dispersive XRF (EDXRF) (three measurements per naphtha length Dispersive X-ray Fluorescence; Monochromatic X-ray;
sample). One participant measured each washed naphtha fraction by
MWDXRF and MEDXRF, and one participant measured each washed MWDXRF; naphtha; organic chloride; organo-chlorine; polar-
naphtha fraction once by MWDXRF and twice by MEDXRF using two ization; sodium biphenyl; spectrometry; X-ray; X-ray Fluores-
MEDXRF analyzers manufactured by two vendors. The participant total cence; XRF
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14
D4929 − 19
FIG. 2 Average Recovery of Organic Chloride Spikes by XRF
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.
MNL79). However, when it is demonstrated that the testing is under
statistical control, the QC testing frequency may 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 process8 (see Practice
D6299 and MNL79). 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
may, 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 must be
test method, the frequency of QC testing is dependent on the homogeneous and stable under the anticipated storage condi-
tions.
9
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 MNL79 for further guidance
PA. on QC and control charting techniques.
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15
D4929 − 19
X2. CAUTION REGARDING CRUDE OIL SAMPLE PREPARATION USING WATER WASHING
X2.1 Under certain conditions, salt (inorganic chlorides Removal of inorganic salts prior to analysis can provide “false
such as MgCl2 and CaCl2) contained within many crude oils negative” results when considering refinery operations. The
can undergo hydrolysis during the Test Method D86 distillation user of the method should consider how the data is to be used
step used to isolate the <204 °C fraction for analysis. The before choosing to implement a pre-distillation water wash. It
hydrolysis results in the formation of hydrochloric acid (HCl), is advised to conduct the method as written, without pre-
which can subsequently react with available organic chloride distillation wash. Then, if deemed necessary, conduct the
precursors such as olefins, alcohols, and esters that are present evaluation with the pre-distillation water wash in place, and
in the naphtha fraction, and form organic chlorides. These report both results.
formed organic chlorides remain in the naphtha fraction and
are reported in the final test result. As a result, some users have X2.3 In the event that a sample was prepared for Test
adopted the practice of water washing neat crude samples prior Method D4929 testing by water washing the neat crude, the
to distillation, in order to remove what is often deemed a reported results shall include a statement indicating what
potential interference. sample preparation technique was employed, such as
“D4929A-Modified with Crude Pre-Wash.”
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 Test Method D4929 permits water washing of
simulates the conditions of an atmospheric crude distillation the distilled naphtha, it does not include neat sample prepara-
tower. Any organic chlorides that are present in the naphtha tion by water washing of the crude oil sample prior to testing,
pose a risk to refinery operations. Therefore, their presence or and the information provided in this appendix shall not be
absence in the Test Method D4929 test results are relevant. interpreted as support for this preparation practice.
SUMMARY OF CHANGES
Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D4929 – 17) that may impact the use of this standard. (Approved July 1, 2019.)
(1) Revised subsections 1.6.1, 23.1, 23.2.1, 23.2.2, 23.3.1, (5) Revised Note 8.
23.3.2, 23.4.1, 23.4.4, 23.5.2, 23.5.3, 24.6, 25.7, 27.1, 27.1.2, (6) Removed Table 1 Recommended Chlorine (mg/kg) Stan-
28.6, 30.1, 30.1.1, 30.2, 32.1.1.1, 32.1.1.2, 32.1.1.3, 32.1.2.1, dard Calibration Ranges and renumbered subsequent tables.
32.1.2.2, and 32.1.2.3. (7) Replaced Table 3 Calculated Precision Values, Procedure C
(2) Deleted subsections 23.2.7, 23.3.5, and 23.4.6. XRF with Table 2 and Table 3 which contain calculated
(3) Added subsection 23.5.1 and renumbered rest of section. precision values for all procedures.
(4) Added Note 7 and Note 9, and renumbered subsequent
notes.
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of infringement of such rights, are entirely their own responsibility.
This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
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ASTM D4929-Organic Chloride

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This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

Standard Test Method for

1. Scope* mendations issued by the World Trade Organization Technical

*A Summary of Changes section appears at the end of this standard

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16.1 Use extreme care to prevent contamination. Reserve all where:

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where: 28.6 For MEDXRF spectrometers, determine the peak area

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FIG. 2 Average Recovery of Organic Chloride Spikes by XRF

X1. GENERIC QUALITY CONTROL STATEMENT FOR D02 TEST METHODS

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