ASTM D4929-17 Cloruro Orgánico

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 − 17
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* 2. Referenced Documents

1.1 The procedures in this test method cover the determi- 2.1 ASTM Standards:2
nation of organic chloride (above 1 µg/g organically-bound D86 Test Method for Distillation of Petroleum Products and
chlorine) in crude oils, using either distillation and sodium Liquid Fuels at Atmospheric Pressure
biphenyl reduction, distillation and microcoulometry, or distil- D1193 Specification for Reagent Water
lation and x-ray fluorescence (XRF) spectrometry. D4057 Practice for Manual Sampling of Petroleum and
1.2 The procedures in this test method involve the distilla- Petroleum Products
tion of crude oil test specimens to obtain a naphtha fraction D4177 Practice for Automatic Sampling of Petroleum and
prior to chloride determination. The chloride content of the Petroleum Products
naphtha fraction of the whole crude oil can thereby be D6299 Practice for Applying Statistical Quality Assurance
obtained. See Section 5 regarding potential interferences. and Control Charting Techniques to Evaluate Analytical
Measurement System Performance
1.3 Procedure A covers the determination of organic chlo- D6300 Practice for Determination of Precision and Bias
ride in the washed naphtha fraction of crude oil by sodium Data for Use in Test Methods for Petroleum Products and
biphenyl reduction followed by potentiometric titration. Lubricants
1.4 Procedure B covers the determination of organic chlo- D6708 Practice for Statistical Assessment and Improvement
ride in the washed naphtha fraction of crude oil by oxidative of Expected Agreement Between Two Test Methods that
combustion followed by microcoulometric titration. Purport to Measure the Same Property of a Material
1.5 Procedure C covers the determination of organic chlo- D7343 Practice for Optimization, Sample Handling,
ride in the washed naphtha fraction of crude oil by x-ray Calibration, and Validation of X-ray Fluorescence Spec-
fluorescence spectrometry. trometry Methods for Elemental Analysis of Petroleum
Products and Lubricants
1.6 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 3. Summary of Test Method
standard.
3.1 A crude oil distillation is performed to obtain the
1.6.1 The preferred concentration units are micrograms of
naphtha cut at 204 °C (400 °F). The distillation method was
chloride per gram of sample.
adapted from Test Method D86 for the distillation of petroleum
1.7 This standard does not purport to address all of the products. The naphtha cut is washed with caustic, repeatedly
safety concerns, if any, associated with its use. It is the when necessary, until all hydrogen sulfide is removed. The
responsibility of the user of this standard to establish appro- naphtha cut, free of hydrogen sulfide, is then washed with
priate safety, health, and environmental practices and deter- water, repeatedly when necessary, to remove inorganic halides
mine the applicability of regulatory limitations prior to use. (chlorides).
1.8 This international standard was developed in accor-
dance with internationally recognized principles on standard- 3.2 There are three alternative procedures for determination
ization established in the Decision on Principles for the of the organic chloride in the washed naphtha fraction, as
Development of International Standards, Guides and Recom- follows.
mendations issued by the World Trade Organization Technical 3.2.1 Procedure A, Sodium Biphenyl Reduction and
Barriers to Trade (TBT) Committee. Potentiometry—The washed naphtha fraction of a crude oil
specimen is weighed and transferred to a separatory funnel
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 Oct. 15, 2017. Published December 2017. Originally contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
approved in 1989. Last previous edition approved in 2016 as D4929 – 16. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D4929-17. 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
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D4929 − 17
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
refining operations as the organic chlorides.
—The washed naphtha fraction of a crude oil specimen is
injected into a flowing stream of gas containing about 80 % 4.3 Organic chloride species are potentially damaging to
oxygen and 20 % inert gas, such as argon, helium, or nitrogen. refinery processes. Hydrochloric acid can be produced in
The gas and sample flow through a combustion tube main- hydrotreating or reforming reactors and the acid accumulates in
tained at about 800 °C. The chlorine is converted to chloride condensing regions of the refinery. Unexpected concentrations
and oxychlorides, which then flow into a titration cell where of organic chlorides cannot be effectively neutralized and
they react with the silver ions in the titration cell. The silver damage can result. Organic chlorides are not known to be
ions thus consumed are coulometrically replaced. The total naturally present in crude oils and usually result from cleaning
current required to replace the silver ions is a measure of the operations at producing sites, pipelines, or tanks. It is important
chlorine present in 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
generated coulometrically thus: 5.1 Procedure A—Other titratable halides will also give a
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
fluorescence (MWDXRF), monochromatic energy dispersive 5.3 Procedure C—X-ray fluorescence spectrometry tech-
x-ray fluorescence (MEDXRF), or energy dispersive x-ray niques may have interferences due to high sulfur content and
fluorescence (EDXRF) spectrometry. The resulting net count- matrix effects due to differences in the carbon-hydrogen ratio.
ing rate is then compared to a previously prepared calibration 5.3.1 Matrix effects result when the elemental composition
curve or equation to obtain the concentration of chlorine in (excluding chlorine) of samples differs significantly from the
mg/kg. standards, and significant errors in the chlorine determination
can result. For example, differences in the carbon-hydrogen
4. Significance and Use ratio of sample and calibration standards introduce errors in the
4.1 Organic chlorides do not occur naturally in crude oil. determination.
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When present, they result from contamination in some manner, 5.3.2 In general, naphthas with compositions that vary from
such as disposal of chlorinated solvent used in many dewaxing white oils as specified in 27.1 can be analyzed with standards
pipeline or other equipment operations. made from base materials that are of the same or similar
4.1.1 Uncontaminated crude oil will contain no detectable composition. A base material for naphtha may be simulated by
organic chloride, and most refineries can handle very small mixing isooctane and toluene in a ratio that approximates the
amounts without deleterious effects. expected aromatic content of the samples to be analyzed.
4.1.1.1 Most trade contracts specify that no organic chloride 5.3.3 Naphtha samples may contain high amounts (≥0.5
is present in the crude oil. mass %) of sulfur leading to significant absorption of chlorine
4.1.2 Several pipelines have set specification limits at Kα radiation and low chlorine results. Such samples can,
<1 mg ⁄kg organic chlorides in the whole crude, and <5 mg ⁄kg however, be analyzed using this test method provided either
in the light naphtha, on the basis of the naphtha fraction being that the calibration standards are prepared to match the matrix
20 % of the original sample. of the sample or correction factors are applied to the results. In
4.1.2.1 To ensure <1 mg ⁄kg organic chloride in the crude some cases, dilution of samples with sulfur-free and chlorine-
oil, the amount measured in the naphtha fraction shall be <1/f free oil can be used to reduce the effect. The main disadvantage
(where f is the naphtha fraction calculated with Eq 3). is, however, that dilution also lowers the amount of chlorine in

D4929 − 17
the specimen. Make sure that in the diluted specimen, the 7.6 Vacuum Take-Off Adapter, borosilicate, 105° angle bend,
chlorine content is higher than 1 mg/kg before resorting to 24/40 ground-glass joints.
dilution. 7.7 Receiving Cylinder, borosilicate, 250 mL capacity, 24/40
5.3.4 Matrix matching requires the knowledge of typical outer ground-glass joint.
sulfur concentration in the naphtha sample and preparing
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 7.9 Receiver Flask, for ice bath, 4 L.
samples. 7.10 Copper Tubing, for heat exchanger to cool condenser
5.3.5 Sulfur correction factors are typically applied by using water, 6.4 mm outside diameter, 3 m length.
the software and algorithms supplied by the equipment vendor
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, 7.12 Variacs, 2, for temperature control of upper and lower
correction by use of Compton scattering, and correction by heating elements, 120 V, 10 amps.
applying fundamental parameters. Follow manufacturer’s in-
structions for application of sulfur correction factors and when 8. Reagents and Materials
to apply those factors. 8.1 Acetone, chloride-free. (Warning—Extremely
flammable, can cause flash fires. Health hazard.)
6. Purity of Reagents
8.2 Caustic Solution, 1 M potassium hydroxide
6.1 Purity of Reagents—Reagent grade chemicals shall be (Warning—Can cause severe burns to skin.) prepared in
used in all tests. Unless otherwise indicated, it is intended that distilled/deionized water.
all reagents shall conform to the specifications of the Commit-
tee on Analytical Reagents of the American Chemical Society, 8.3 Distilled/Deionized Water.
where such specifications are available.3 Other grades may be 8.4 Filter Paper, Whatman No. 41 or equivalent.
used, provided it is first ascertained that the reagent is of 8.5 Stopcock Grease.4,5
sufficiently high purity to permit its use without lessening the
accuracy of the determination. 8.6 Toluene, chloride-free. (Warning—Flammable. Health
hazard.)
6.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean reagent water as defined 9. Sampling
by Type III of Specification D1193. 9.1 Obtain a test unit in accordance with Practice D4057 or
DISTILLATION AND CLEANUP PROCEDURE D4177. To preserve volatile components, which are in some
samples, do not uncover samples any longer than necessary.
7. Apparatus Samples should be analyzed as soon as possible, after taking
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
7.2 Tee Adapter, borosilicate, 75° angle side-arm, 24/40 below room temperature may undergo expansion and rupture
ground-glass joints. the container. For such samples, do not fill the container to the
7.3 Thermometer, ASTM thermometer 2C (–5 °C to 300 °C) top; leave sufficient air space above the sample to allow room
or 2F, (20 °F to 580 °F). for expansion.)
7.3.1 Other temperature measuring devices, such as thermo- 9.2 If the test unit is not used immediately, then thoroughly
couples or resistance thermometers, may be used when the mix in its container prior to taking a test specimen. Some test
temperature reading obtained by these devices is determined to units can require heating to thoroughly homogenize.
produce the same naphtha fraction that is obtained when (Warning—When heating is required, care should be taken so
mercury-in-glass thermometers are used. that no organic chloride containing hydrocarbons are lost.)
7.4 Thermometer Adapter, borosilicate, 24/40 inner ground-
10. Preparation of Apparatus
glass joint.
10.1 Clean all glassware by rinsing successively with tolu-
7.5 Liebig Condenser, borosilicate, 300 mm length, 24/40
ene and acetone. After completing the rinse, dry the glassware
ground-glass joints.
using a stream of dry nitrogen gas. Obtain and record the
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 − 17
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
such that the lower end of the capillary is level with the highest 12. Calculation
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
the copper coil to the water source, and connect the other end 12.2 Calculate the density as follows:
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
water. Maintain the temperature of the condenser below 10 °C. m = mass of sample specimen, g, and
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
apparatus. Place the heating mantle around the flask, and 13.1 Electrodes—The cleaning and proper care of electrodes
support the heating mantle/flask from the bottom. Connect the are critical to the accuracy of this test. Manufacturer’s instruc-
heating mantle to the variacs. Turn on the variacs and start the tions for the care of electrodes shall be followed.
distillation. During the distillation, adjust the variac settings to 13.1.1 Glass, general purpose. When glass electrodes are in
give a distillation rate of approximately 5 mL ⁄min. Continue continuous use, weekly cleaning with chrome-sulfuric acid
the distillation until a thermometer reading of 204 °C (400 °F) (Warning—Strong oxidizer; can cause severe burns; recog-
is attained. When the temperature reaches 204 °C (400 °F), end nized carcinogen), or other strongly oxidizing cleaning
the distillation by first disconnecting and removing the receiv- solution, is recommended.
ing cylinder. After the receiving cylinder has been removed, 13.1.2 Silver-Silver Chloride, billet-type.
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.
11.1.1 The precision and bias statements were determined 14. Reagents and Materials
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-
in-glass thermometers are used. Such alternate temperature 14.3 2,2,4, trimethyl pentane (isooctane), reagent grade.
measuring devices shall not be expected to exhibit the same (Warning—Flammable. Health hazard.)
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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
11.2 Transfer the naphtha fraction from the receiving cylin- nitric acid to about 200 mL of water and dilute to 500 mL.
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.
The caustic wash removes hydrogen sulfide, while the water 14.7 Sodium Biphenyl Reagent5,6—This is packed in 0.5 oz
wash removes traces of inorganic chlorides either originally French square bottles (hereafter referred to as vials). The entire
present in the crude or from impurities in the caustic solution. contents of one vial are used for each analysis. One vial
After the washings are complete, filter the naphtha fraction to contains 13 meq to 15 meq of active sodium. Store the sodium
remove residual freestanding water. Store the naphtha fraction biphenyl reagent in a cool storage area, but do not refrigerate.
in a clean glass bottle. This naphtha fraction can now be
analyzed for organic chlorides by either sodium biphenyl, 6
The sole source of supply of the sodium biphenyl reagent known to the
combustion/microcoulometric techniques, or x-ray fluores- committee at this time is Southwestern Analytical Chemicals, P.O. Box 485, Austin,
cence spectrometry. TX.

D4929 − 17
Prior to using, warm the reagent to approximately 50 °C and semi-micro 5 mL piston buret. If the titration is carried out with
shake thoroughly to ensure a homogeneous liquid. 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
plotting the data showing emf versus volume of silver nitrate
15. Preparation of Apparatus 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 16.7 Determine a blank for each group of test specimens by
with mild detergent and scouring powder. Rinse the electrodes using all of the reagents, including the sodium biphenyl, and
in distilled water. Immerse the metallic tips in saturated following all the operations of the analysis except that the
potassium chloride solution. Connect one electrode to the sample itself is omitted.
positive pole of a 1.6-V battery and the other to the negative
pole. Reverse the polarity for several intervals of a few seconds 17. Calculation
each to alternately clean and recoat the receptor electrode 17.1 Calculate chloride concentration in the naphtha frac-
(connected to the positive pole). When adequately coated, the tion as follows:
receptor electrode tip will turn violet in color. This results from
the action of light on the fresh silver chloride. ~ A 2 B ! ~ M ! ~ 35 460!
Chloride, µg/g 5 (5)
W
16. Procedure
where:
16.1 Use extreme care to prevent contamination. Reserve all A = volume of titrant for the sample specimen, mL,
glassware for the chloride determination. Rinse glassware with B = volume of titrant for the blank, mL,
distilled water followed by acetone just prior to use. Avoid M = molarity of silver nitrate, and
using chlorine-containing stopcock greases such as chlorotrif- W = mass of sample specimen, g.
luoroethylene polymer grease.
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17.2 The concentration of organic chloride in the original
16.2 Place 50 mL of toluene in a 250 mL separatory funnel crude oil sample specimen can be obtained by multiplying the
and add the contents of one vial of sodium biphenyl reagent. chloride concentration in the naphtha fraction (see 17.1) by the
Swirl to mix and add about 30 g, obtaining the mass to the naphtha fraction (see 12.1).
nearest 0.1 g of the washed naphtha fraction of crude oil
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 18.1 Combustion Furnace—The sample specimen is to be
or suspension is blue-green. 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 18.2 Combustion Tube—Fabricated from quartz and con-
the funnel unstoppered for a time until the blue-green color structed so a sample, which is vaporized completely in the inlet
changes to white, indicating that no free sodium remains. section, is swept into the oxidation zone by an inert gas where
Stopper the funnel and rock it gently, venting pressure fre- it mixes with oxygen and is burned. The inlet end of the tube
quently through the stopcock. Then add 20 mL of water and shall hold a septum for syringe entry of the sample and side
10 mL of 5 M nitric acid. Shake gently, releasing the pressure arms for the introduction of oxygen and inert gases. The center
frequently through the stopcock. Test the aqueous phase with section is to be of sufficient volume to ensure complete
Congo red paper. If the paper does not turn blue, add additional oxidation of the sample.
5 M nitric acid in 5 mL portions until the blue color is obtained. 18.3 Titration Cell—Containing a sensor-reference pair of
16.4 Drain the aqueous phase into another separatory funnel electrodes to detect changes in silver ion concentration and a
containing 50 mL of isooctane and shake well. Drain the generator anode-cathode pair of electrodes to maintain constant
aqueous phase into a 250 mL titration beaker. Make a second silver ion concentration and an inlet for a gaseous sample from
extraction of the isooctane phase with 25 mL of water that has the pyrolysis tube. The sensor, reference, and anode electrodes
been acidified with a few drops of 5 M nitric acid. Add this shall be silver electrodes. The cathode electrode shall be a
second extract to the 250 mL titration beaker. Evaporate the platinum wire. The reference electrode resides in a saturated
solution on a hot plate kept just below the boiling point of the silver acetate half-cell. The electrolyte contains 70 % acetic
liquid until 25 mL to 30 mL remains. Do not boil or evaporate acid in water.
to less than 25 mL as loss of chloride may occur. 18.4 Microcoulometer, having variable gain and bias
16.5 Cool the solution and add 100 mL of acetone. Titrate control, and capable of measuring the potential of the sensing-
the solution potentiometrically with standard 0.01 M silver reference electrode pair, and of comparing this potential with a
nitrate, using glass versus silver-silver chloride electrodes. If bias potential, and of applying the amplified difference to the
an automatic titrator, such as a Metrohm, is available, use the working-auxiliary electrode pair so as to generate a titrant. The

D4929 − 17
microcoulometer output signal shall be proportional to the 20.2 The typical operational conditions are as follows:
generating current. The microcoulometer may have a digital Reactant gas flow, O2 160 mL/min
meter and circuitry to convert this output signal directly to Carrier gas flow 40 mL/min
Furnace temperature:
nanograms or micrograms of chloride. Inlet zone 700 °C
18.5 Sampling Syringe—A microlitre syringe of 50 µL ca- Center and outlet zones 800 °C
Coulometer:
pacity capable of accurately delivering 5 µL to 50 µL of sample Bias voltage, mV 240–265
into the pyrolysis tube. A 3 in. or 6 in. (76.2 mm or 152.4 mm) Gain ca. 1200
needle is recommended to reach the inlet zone of approxi- 20.3 Optimize the bias voltage setting for the titration cell
mately 500 °C in the combustion zone. null-point by injecting 30 µL of chloride-free water directly
18.6 A constant rate syringe pump or manual dispensing into the titration cell using a 6 in. needle. Adjust bias up or
adaptor may be used to facilitate slow injection of the sample down to minimize the total integrated value due to this dilution
into the combustion tube. It is recommended that the injection effect.
rate not exceed 0.5 µL ⁄s.
21. Procedure
19. Reagents and Materials
21.1 Fill a 50 µL syringe with about 30 µL to 40 µL of the
19.1 Acetic Acid, glacial acetic acid. (Warning—Corrosive, sample of washed naphtha fraction of crude oil, being careful
causes severe burns.) to eliminate bubbles. Then retract the plunger so that the lower
19.2 Argon, Helium, Nitrogen, or Carbon Dioxide, high liquid meniscus falls on the 5 µL mark, and record the volume
purity grade (HP) used as the carrier gas. (Warning—These of liquid in the syringe. After the sample has been injected,
gases are normally stored in cylinders under high pressure. again retract the plunger so that the lower liquid meniscus falls
These gases also dilute the oxygen content of the surrounding on the 5 µL mark, and record the volume of liquid in the
air when they leak.) syringe. The difference in the two volume readings is the
19.3 Cell Electrolyte Solution, 70 % acetic acid, combine volume of sample injected.
300 mL reagent water (see 6.2) with 700 mL acetic acid (see 21.2 Alternately, obtain the sample injection device mass
19.1) and mix well. before and after injection to determine the amount of sample
19.4 Chloride, Standard Stock Solution, 1000 mg chloride injected. This method provides greater precision than the
per litre. Accurately dispense 1.587 g of chlorobenzene into a volume delivery method, provided a balance with a precision
500 mL volumetric flask and dilute to volume with 2,2,4, of 60.01 mg is used and the syringe is carefully handled to
trimethyl pentane (isooctane). obtain repeatable weighings.
NOTE 2—The exact concentration of chloride may be determined by 21.3 Inject the sample into the pyrolysis tube at a rate not to
multiplying the mass of chlorobenzene by the product of the atomic mass exceed 0.5 µL ⁄s.
of chlorine divided by the molecular mass of chlorobenzene and then
multiplying that result by 2000. 21.4 Below 5 µg ⁄g, the needle-septum blank will become
increasingly more obvious. To improve precision, insert the
w 3 m 1 3 2000
Cl ~ mg/ L ! 5 (6) syringe needle into the hot inlet and then wait until the
m2
needle-septum blank is titrated before injecting the sample or
where: standard.
w = mass of chlorobenzene weighed, 21.5 For specimens containing more than 25 µg ⁄g Cl only
m1 = atomic mass of chlorine, and 5.0 µL of sample need be injected.
m2 = molecular mass of chlorobenzene.
21.6 Verify the system recovery, the fraction of chlorine in
19.5 Chlorine, Standard Solution, 10 mg chloride per litre. the standard that is titrated, every 4 h by using the standard
Pipet 1.0 mL of chloride stock solution (see 19.4) into a solution (see 19.5). System recovery is typically 85 % or better.
100 mL volumetric flask and dilute to volume with 2,2,4,
trimethyl pentane (isooctane). 21.7 Repeat the measurement of the calibration standard at
least three times.
19.6 Chlorobenzene, reagent grade.
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).
19.10 Silver Acetate, powder purified for saturated reference
electrode. 22. Calculation
22.1 Calculate chloride concentration in the naphtha frac-
20. Preparation of Apparatus tion as follows:
20.1 Set up the analyzer in accordance with the equipment 22.1.1 For microcoulometers, which read directly in nano-
manufacturer instructions. grams of chloride, the following equations apply:
--`,,,`,,,,`,`,`,`,``,,`-`-``,```,,,`---

D4929 − 17
Sample Readout Blank Readout producing Pd Lα, Ag Lα, Ti Kα, Sc Kα, and Cr Kα radiation are
Chloride, µg/g 5 2 (7)
~ V ! ~ D ! ~ RF! ~ V ! ~ D ! ~ RF! recommended for this purpose. (Warning—Exposure to ex-
cessive quantities of high energy radiation such as those
or
produced by X-ray spectrometers is injurious to health. The
Sample Readout Blank Readout operator needs to take appropriate actions to avoid exposing
Chloride, µg/g 5 2 (8)
~ M ! ~ RF! ~ M ! ~ RF! any part of their body, not only to primary X-rays, but also to
where: secondary or scattered radiation that might be present. The
X-ray spectrometer should be operated in accordance with the
Readout = displayed integrated value (sample/standard/
regulations governing the use of ionizing radiation.)
blank),
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 atmosphere. If vacuum is used, a level of
standard divided by known standard content mi- lower than 2.7 kPa (<20 Torr) is recommended. If helium is
nus the system blank. used, it is recommended to limit variations in pressure and
temperature to within 10 % relative. The calibration and test
Standard Readout Blank Readout
RF 5 2 measurements must be done with identical optical paths,
~ V ! ~ D ! ~ C s! ~ V ! ~ D ! ~ C s!
including vacuum or helium pressure.
M = mass of sample specimen, mg, and 23.2.3 Incident-beam Monochromator, capable of focusing
Cs = concentration of standard, mg/L and selecting a single wavelength of characteristic x-rays from
22.1.2 For microcoulometers with only analog signal output the source onto the specimen.
to a recorder the following equation applies: 23.2.4 Fixed-channel Monochromator, suitable for dispers-
ing chlorine Kα x-rays.
~ A ! ~ X ! ~ 0.367!
Chloride, µg/g 5 2B (9) 23.2.5 Detector, designed for efficient detection of chlorine
~ R ! ~ Y ! ~ M ! ~ RF!
Kα x-rays.
where: 23.2.6 Single-channel Analyzer, an energy discriminator to
A = area in appropriate units, monitor only chlorine radiation.
X = recorder sensitivity for full-scale response, mV, 23.2.7 Display or Printer, that reads out in mg/kg chlorine.
0.367 = ~ 35.45 gCl/eq! ~ 1023 V/mV! ~ 106 µg/g !
23.3 Monochromatic Energy Dispersive X-ray Fluorescence
~ 96 500 coulombs/eq!
(MEDXRF) Spectrometer, including the following:
R = resistance, Ω, 23.3.1 Source of X-ray Excitation, x-ray tube with Ag or Pd
Y = area equivalence for a full-scale response on the anode, in combination with HOPG Bragg monochromating
recorder per second-area units per second, X-ray optics. The monochromator must produce monochro-
M = mass of sample, g, matic Ag or Pd L radiation. Other anode materials and
RF = recovery factor, and monochromators may be utilized, however stated precision and
B = system blank, µg/g Cl. bias may not apply. (Warning—Exposure to excessive quan-
22.2 The concentration of organic chloride in the original tities of high energy radiation such as those produced by X-ray
crude oil sample specimen can be obtained by multiplying the spectrometers is injurious to health. The operator needs to take
chloride concentration in the naphtha fraction (see 22.1) by the appropriate actions to avoid exposing any part of their body,
naphtha fraction (see 12.1). not only to primary X-rays, but also to secondary or scattered
radiation that might be present. The X-ray spectrometer should
PROCEDURE C—X-RAY FLUORESCENCE be operated in accordance with the regulations governing the
SPECTROMETRY use of ionizing radiation.)
23.3.2 Optical Path, the system must allow flushing of the
23. Apparatus
optical path with helium (see 24.6). When connecting a new
23.1 Any spectrometer of the following type: Monochro- helium gas cylinder, always run a blank measurement to ensure
matic Wavelength Dispersive X-ray Fluorescence (MWDXRF) the helium gas line is purged of air. Alternatively, a vacuum of
Spectrometer, Monochromatic Energy Dispersive X-ray Fluo- ≤4.0 kPa (≤30.4 Torr) is applied to the optical path. If helium
rescence (MEDXRF) Spectrometer, or Energy Dispersive X-ray is used, it is recommended to limit variations in pressure and
Fluorescence (EDXRF) Spectrometer can be used if it includes temperature to within 10 % relative. When the air in the optical
the following features for its type described in this section and path is relatively small, then vacuum or helium may be
the precision and bias of the test results are in accordance with optional. Follow manufacturer’s recommendations.
the values for its type described in Section 32. 23.3.3 X-ray Detector, with a resolution value not to exceed
--`,,,`,,,,`,`,`,`,``,,`-`-``,```,,,`---
23.2 Monochromatic Wavelength Dispersive X-ray Fluores- 175 eV at 5.9 keV (10 000 cps). A Si drift chamber detector
cence (MWDXRF) Spectrometer, equipped for x-ray detection (SDD) has been found suitable for use. Using a detection
at 0.473 nm (4.73A) which also includes the following: system with this minimum spectral resolution has been shown
23.2.1 X-ray Source, capable of producing X-rays to excite to eliminate the potential effect of spectral interference from
chlorine. X-ray tubes with a power of >20W capable of sulfur or other elements in the naphtha sample.

D4929 − 17
23.3.4 Signal Conditioning and Data Handling Electronics, 24. Reagents and Materials
including the functions of x-ray intensity counting, spectra 24.1 Purity of Reagents—Reagent grade chemicals shall be
handling by background subtraction and deconvolution, calcu- used in all tests. Unless otherwise indicated, it is intended that
lation of overlap corrections and conversion of chlorine X-ray all reagents conform to the specifications of the Committee on
intensity into mg/kg chlorine concentration. Analytical Reagents of the American Chemical Society where
23.3.5 Display or Printer, that reads out in mg/kg chlorine. such specifications are available.7 Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently
23.4 Energy Dispersive X-ray Fluorescence (EDXRF)
high purity to permit its use without lessening the accuracy of
Spectrometer, required design features include:
the determination.
23.4.1 Source of X-ray Excitation, X{ray tube with excita-
tion energy above 2.9 keV. (Warning—Exposure to excessive 24.2 Calibration Check Samples, portions of one or more
quantities of high energy radiation such as those produced by liquid petroleum or product standards of known or certified
chlorine content and not used in the generation of the calibra-
x-ray spectrometers is injurious to health. The operator needs
tion curve. The check samples shall be used to determine the
to take appropriate actions to avoid exposing any part of their
precision and accuracy of the initial calibration (see 27.6).
body, not only to primary X-rays, but also to secondary or
scattered radiation that might be present. The X-ray spectrom- 24.3 Chlorine Dopant (CD), a high{purity standard with a
eter should be operated in accordance with the regulations certified chlorine content. Trichloroethylene and 1,2,4-
governing the use of ionizing radiation.) trichlorobenzene have been found to be acceptable chlorine
23.4.2 X-ray Detector, with high sensitivity and a resolution dopants. Use the certified chlorine concentration when calcu-
lating the exact concentrations of chlorine in calibration
value (Full Width at Half Maximum, FWHM) not to exceed
standards. (Warning—Breathing trichloroethylene vapors may
175 eV at 5.9 keV (10 000 cps). A Si drift chamber detector
cause drowsiness and dizziness. Causes eye and skin irritation.
(SDD) has been found suitable for use.
Aspiration hazard if swallowed. Can enter lungs and cause
23.4.3 Filters, or other means of discriminating between damage. May cause cancer based on animal studies. May cause
chlorine Kα radiation and other x-rays of different energy. The liver damage.) (Warning—1,2,4-trichlorobenzene may cause
other means include software solutions. respiratory tract irritation. Harmful if swallowed. Causes eye
23.4.4 Optical Path, the system must allow flushing of the and skin irritation.)
optical path with helium (see 24.6). When connecting a new
24.4 Counting Gas, for instruments equipped with flow
helium gas cylinder, always run a blank measurement to ensure proportional counters. The purity of the counting gas should be
the helium gas line is purged of air. Alternatively, a vacuum of in agreement with the specification provided by the instrument
≤4.0 kPa (≤30.4 Torr) is applied to the optical path. If helium manufacturer.
is used, it is recommended to limit variations in pressure and
temperature to within 10 % relative. 24.5 Drift Correction Monitor(s) (Optional)—Several dif-
ferent materials have been found to be suitable for use as drift
23.4.5 Signal Conditioning and Data Handling Electronics,
correction monitors. Appropriate drift monitor samples should
that include the functions of x-ray intensity counting, a
be permanent materials that are stable with respect to repeated
minimum of two energy regions, spectral overlap corrections,
exposure to x-rays. Stable liquids, glass or metallic specimens
background corrections, and conversion of chlorine x-ray
are recommended. Liquids, pressed powders, and solid mate-
intensity into mass percent chlorine concentration.
rials that degrade with repeated exposure to x-rays should not
23.4.6 Display or Printer, that reads out in mg/kg chlorine. be used. Examples of chlorine containing materials that have
23.5 Additionally, the following apparatus is needed when been found to be suitable include a renewable liquid petroleum
using all x{ray spectrometers within the scope of this method: material, a metal alloy, or a fused glass disk. The monitor’s
counting rate, in combination with count time, shall be
23.5.1 Removable Sample Cell, an open{ended specimen
sufficient to give a relative counting error of less than 1 %. The
holder compatible with the sample and the geometry of the
counting rate for the monitor sample is determined during
XRF spectrometer. A disposable cell is recommended. The
calibration (see 27.4) and again at the time of analysis (see
sample cell should not leak when fitted with x-ray transparent
28.1). These counting rates are used to calculate a drift
film (see 23.5.2). correction factor (see 29.1).
23.5.2 X-ray Transparent Film, for containing and support-
ing the test specimen in the sample cell (see 23.5.1) while NOTE 3—Calibration standards may be used as drift{monitor samples.
Because it is desirable to discard test specimens after each determination,
providing a low{absorption window for X-rays to pass to and a lower cost material is suggested for daily use. Any stable material can be
from the sample. Any film resistant to chemical attack by the
--`,,,`,,,,`,`,`,`,``,,`-`-``,```,,,`---
used for daily monitoring of drift.

sample, free of chlorine, and X-ray transparent can be used, for
example, polyester, polypropylene, polycarbonate, and poly-
imide. However, samples of high aromatic content can dissolve 7
Reagent Chemicals, American Chemical Society Specifications, American
polyester and polycarbonate films. Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
23.5.3 Analytical Balance, for preparing calibration listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
standards, capable of weighing to the nearest 0.1 mg and up to and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
100 g. MD.

D4929 − 17
NOTE 4—The effect of drift correction on the precision and bias of this analyzer may need recalibration if the type or thickness of the
test method has not been studied. window film is changed.
24.5.1 Drift correction is usually implemented automati- 25.5 Place the sample in the cell using techniques consistent
cally in software, although the calculation can readily be done with good practice for the particular instrument being used.
manually. For X-ray instruments that are highly stable, the Although chlorine radiation will emerge from only a small
magnitude of the drift correction factor may not differ signifi- distance into the sample, scatter from the sample cell and the
cantly from unity. sample can vary. Laboratory personnel shall ensure that the
24.6 Helium Gas, for instruments equipped with a helium sample cell is filled above a minimum depth, beyond which
optical path (optional for some analyzers). The minimum additional sample does not significantly affect the count rate.
purity 99.9 %. Generally, fill the sample cell to a minimum of one-half of the
cell’s capacity. After the sample cell is filled and film is
24.7 Quality Control Samples, stable petroleum or product attached, provide a vent above the sample to prevent bowing of
samples or solids representative of the samples of interest that the film by accumulating vapors.
are run on a regular basis to verify that the system is in
statistical control (see Section 31). 25.6 Ensure the sample is not leaking after preparation, and
perform the analysis of the specimen promptly after preparing
NOTE 5—Verification of system control through the use of QC samples the specimen. Do not let the specimen remain in the sample
and control charting is highly recommended. It is recognized that QC
procedures are the province of the individual laboratory.
cell any longer than necessary before collecting the data.
NOTE 6—Suitable QC samples can often be prepared by combining 25.7 If the MEDXRF instrument (see 23.3) is equipped with
retains of typical samples if they are stable. QC samples must be stable a replaceable secondary/safety window, it should be checked
over long periods. periodically and changed if it is wrinkled, ripped, dirty, or
24.8 White Mineral Oil (WMO), ACS Reagent Grade con- contaminated by a leaking sample cup. When changing the
taining less than 1 mg/kg chlorine or other suitable base 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 26. Preparation of Apparatus
certified, verify the absence of chlorine. Use the purest grades 26.1 Ensure that the XRF analyzer has been installed and
for the preparation of calibration standards. It is also important put into operation according to manufacturer’s instructions.
to measure and correct for the C/H ratio (see Section 29.7), if Allow sufficient time for instrument electronics to stabilize.
it differs significantly from the calibration standards when Perform any instrument checkout procedures required. When
calculating the final results. possible, the instrument should be run continuously to maintain
optimum stability.
25. Sampling and Specimen Preparation 26.1.1 Use the count time (T) recommended by the instru-
25.1 Samples shall be taken in accordance with the instruc- ment manufacturer for the lowest chlorine concentration ex-
tions in Practices D4057 or D4177 when applicable. pected.
25.2 When reusable sample cells are used, clean and dry 27. Calibration
cells before each use. Disposable sample cells shall not be
27.1 Prepare a set of calibration standards bracketing the
reused. For each sample, an unused piece of X-ray film is
expected concentration range in the samples by careful mass
required for the sample cell. Avoid touching the inside of the
dilution of a chlorine dopant (CD, see 24.3) with a chlorine{
sample cell, the portion of the window film in the cell, or the
free white mineral oil (WMO, see 24.8) or other suitable base
instrument window (if the instrument is so equipped) that is
material. Trichloroethylene and 1,2,4-trichlorobenzene have
exposed to X-rays. Oil from fingerprints can affect the reading
been found to be suitable chlorine dopants (see 24.3). The
when analyzing for low levels of chlorine. Wrinkles in the film
concentrations of the unknown samples must lie within the
will affect the intensity of the chlorine x-rays transmitted.
calibration range that is used. All standards used in the analysis
Therefore, it is essential that the film be taut and clean to
must be from a reliable and consistent source, which can
ensure reliable results.
include commercially available standards. Recommended
25.3 Use the appropriate film for the sample type. Samples nominal chlorine concentration standards are listed in Table 1.
of high aromatic content may dissolve polyester, polypropyl-
ene and polycarbonate films. In these cases, other materials
besides these films may be used for X-ray windows, provided
that they do not contain any elemental impurities. Follow
instrument manufacturer’s recommendations where possible.
25.4 Because impurities and thickness variations can occur
--`,,,`,,,,`,`,`,`,``,,`-`-``,```,,,`---
in commercially available transparent films and vary from lot

to lot, use calibration-check samples (see 24.2) to verify
calibration integrity after starting each new batch of film. The

D4929 − 17
TABLE 1 Recommended Chlorine (mg/kg) Standard Calibration where:
Ranges
l = net intensity for the chlorine radiation,
NOTE 1—Distillation of the crude oil will concentrate organic chlorides Cl = chlorine concentration in mg/kg,
in the naphtha fraction. For example, the sample with the highest organic m = slope, and
chloride concentration in ILS 1122 was crude sample B (see RR:D02- b = intercept.
1875). This crude oil sample was doped with 12 mg/kg organic chlorides,
and the resulting naphtha fraction measured an average of 55 mg/kg, 60 27.4 When using drift correction monitors, determine the
mg/kg, and 52 mg/kg chlorine respectively for MWDXRF, MEDXRF, and intensity of the drift correction monitor sample(s) during the
EDXRF. Therefore, it is recommended to calibrate the XRF analyzer calibration procedure. The value determined corresponds to the
higher than the expected organic chloride concentration in the crude oil.
factor A in Eq 13 in 29.1.
MWDXRF MEDXRF EDXRF
0A 0A 0A 27.5 A sulfur calibration model may be required for spec-
5 5 5 trometers utilizing a direct sulfur measurement in the sulfur
10 10 10
25 25 25 correction factor. If required, construct a calibration model by
50 50 50 using the software and algorithms supplied by the equipment
100 100 100 vendor. The calibration model may be empirical or make use of
A
Base material. fundamental parameters (refer to the equipment vendor’s
software documentation to determine the exact form).
27.6 Immediately after completing the calibration, deter-
mine the chlorine concentration of one or more of the calibra-
27.1.1 Take into account any chlorine in the base materials tion check samples (24.2). The determined value shall be in the
when calculating the chlorine content (mg/kg) in each of the range defined by the certified concentration plus or minus the
calibration standards as shown in Eq. 10: repeatability of this test method. When this is not the case, the
calibration process and calibration standards are suspect and
Cl 5 @ ~ CD 3 Cl CD ! 1 ~ WMO 3 Cl WMO ! # ⁄ ~ CD 1 WMO!
corrective measures should be taken. The degree of matrix
(10) mismatch between samples and standards should also be
where: considered when evaluating a calibration. Statistical quality
Cl = mass fraction of the chlorine of the prepared control charts may be prepared for these materials to establish
standards, mg/kg, if the method is in statistical control, as described in Section
CD = actual mass of the chlorine dopant, g, 31.
ClCD = the mass fraction of chlorine in the chlorine
dopant, mg/kg, typically 0.8095 mg/kg for trichlo- 28. Procedure
roethylene and 0.861 mg/kg for 1,2,4- 28.1 When using drift correction monitors, before analyzing
--`,,,`,,,,`,`,`,`,``,,`-`-``,```,,,`---
trichlorobenzene, samples on a given day, analyze the drift correction monitor(s)

WMO = actual mass of white mineral oil, g, and and determine the counting rate, using the same material as
ClWMO = mass fraction of chlorine in the white mineral oil, used at the time of calibration. The value determined corre-
mg/kg. sponds to the factor B in 29.1.
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
known and they approximate the nominal recommended con- 28.3 Prepare a test specimen of the sample of interest
centrations listed in Table 1. according to Section 25. Quality control samples shall be
27.1.3 Store all standards and QC samples in glass bottles in prepared and run identically to any unknown sample.
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
sulfur concentration or direct sulfur measurement of the
I 5 Cl*m1b (11) sample. Refer to equipment vendor’s software documentation
Cl 5 l*m1b (12) to determine the exact form of the correction.

10
Order Number: 02233689
D4929 − 17
28.6 For MEDXRF spectrometers, determine the peak area 29.2.1 Calculate the chlorine content (Cl) of the test speci-
of the chlorine Kα radiation at 2.307 keV. The net count{rate men by using the drift{corrected count rate (Icor) in place of I
will be calculated by subtracting the background. The back- in Eq 11 of 27.3. In many cases the instrument vendor will
ground spectrum, measured with a chlorine{free white oil or provide software or the required calculations. The use of the
other matrix matching blank sample (see 24.8) is adapted to the factor F to correct the counting rate of chlorine is optional.
measured spectrum using adjustment regions (see Note 7) 29.3 For MEDXRF spectrometers, the net counting rate, or
following the instrument manufacturer’s instructions and then intensity, is given by the spectral deconvolution of the chlorine
subtracted from the measured spectrum. Determine the cor- Kα line after subtracting the background spectrum.
rected counting rate and calculate the concentration of the 29.3.1 The use of the factor F to correct the counting rate of
sample as described in Section 29. chlorine is optional.
28.6.1 Sulfur Correction MEDXRF—This correction is per- 29.3.2 Calculate the chlorine content (Cl) of the sample by
formed automatically by the analyzer software either by inserting the corrected net counting rate in the calibration Eq
manual input of the sulfur concentration or direct sulfur 12 from 27.3. In many cases the instrument vendor will provide
measurement of the sample. Refer to equipment vendor’s software for the required calculations.
software documentation to determine the exact form of the
correction. 29.4 For EDXRF spectrometers, the concentration of chlo-
rine in the sample is automatically calculated from the calibra-
NOTE 7—When using an Ag or Pd target X{ray tube, background tion curve.
adjustment regions at 2.86{2.92 keV and 2.95{3.04 keV have been found
suitable. 29.5 If the specimens have ≥0.5 mass % sulfur, then it is
28.7 For EDXRF spectrometers, the chlorine concentration recommended that matrix corrections for sulfur be made. In
is automatically calculated from the calibration, using the some systems, the sulfur lines might be interfering with the
instrument software. intensity of chlorine. In that case, line overlap corrections
28.7.1 Sulfur Correction EDXRF—This correction is per- might be required. Manufacturer’s software typically provides
formed automatically by the analyzer software either by a method to correct for matrix effects and interferences. In
manual input of the sulfur concentration or direct sulfur some instances, both matrix correction and correction for
measurement of the sample. Refer to equipment vendor’s interference may be required. In other specimens only one of
software documentation to determine the exact form of the these corrections must be applied, and in other specimens still
correction. no correction at all is required. Follow manufacturer recom-
mendations for applying sulfur correction.
28.8 If the measured intensity for a test specimen is greater
29.6 If the test specimen was prepared from a quantitatively
than the highest count rate in the calibration curve, quantita-
diluted sample, correct the measured concentration for sample
tively dilute a fresh portion of the sample with the base
dilution. The chlorine concentration (Clo) in the original,
material used to prepare the calibration standards. Dilute the
undiluted sample is calculated as follows:
sample so the resultant count rate is within the limits of the
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:
Cld = concentration of chlorine in test specimen of the
29. Calculations
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
calibration standards is white oil, is shown in Eq 16:
where:
Cl C⁄H 5 $ @ 1.195 2 0.0164 ~ C ⁄ H ! whiteoil # ⁄ @ 1.195
F = drift correction factor,
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 where:
B = counting rate of the drift correction monitor as deter-
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 29.7.1 The value for C/H mass ratio is input for each
I = net count rate (or intensity) for test specimen.
unknown sample. The Clwhiteoil will be corrected for the
--`,,,`,,,,`,`,`,`,``,,`-`-``,```,,,`---

D4929 − 17
different C/H ratios. Accordingly, if standards are prepared 31.2 Users of this test method are advised that in contractual
with a different solvent, the C/H ratio for that solvent should be agreements, one or more of the contracting parties can and may
used in place of (C/H)whiteoil. Differences between the C/H ratio make Appendix X1 mandatory practice.
between standards and samples will contribute to error in the 31.3 Additionally, the following QA/QC steps should be
measured result. It is the analyst’s discretion as to when this observed when using Procedure C:
error is large enough to be corrected by Eq 16. If unsure 31.3.1 In addition to running a quality control sample
whether or not to apply correction, follow the analyzer manu- (24.7), it is strongly recommended that the calibration blank be
facturer’s instructions. analyzed on a daily basis.
29.8 The concentration of the organic chloride in the origi- 31.3.1.1 The measured concentration for the blank should
nal crude oil sample specimen can be obtained by multiplying be less than 1 mg/kg chlorine. If the measured concentration
the chlorine concentration in the naphtha fraction, Cl in Eq 11 for the blank is greater than 1 mg/kg, repeat the measurement
and Eq 12 (see 27.3), by the naphtha fraction, f, in Eq 3 (see of the blank (use a fresh sample and fresh cell). If the measured
12.1). concentration of the blank is still greater than 1 mg/kg,
restandardize the instrument and repeat the measurement of the
30. Report blank (use a fresh sample and fresh cell). If the result falls
30.1 Report the organic chloride content of the naphtha outside the acceptable range, carry out a full calibration. If the
fraction in µg/g (or mg/kg) calculated in Eq 5 for Procedure A, sample loading port becomes contaminated, especially when
Eq 7-9 for Procedure B, and/or Section 29 for Procedure C. analyzing <20 mg/kg chlorine level samples, it is necessary to
open and clean it according to manufacturer’s recommenda-
30.2 The organic chloride content of the original crude oil tions before further use.
sample specimen is also expressed as µg/g (or mg/kg) and is 31.3.2 It should be noted that in order to obtain a good fit for
calculated in accordance with 17.2 for Procedure A, 22.2 for the calibration at low concentrations, it may be necessary to
Procedure B, and 29.8 for Procedure C. change the weighting factor in the regression. It may also be
30.3 Indicate that results were determined by Test Method beneficial to change the weighting method used. Many soft-
D4929, Procedure A; Test Method D4929, Procedure B; or Test ware packages default to square root error weighting but have
Method D4929, Procedure C. For Procedure C, also report the possibility of using linear error weighting or no error
whether the result was obtained by MWDXRF, MEDXRF, or weighting.
EDXRF. Denote if method modifications, such as described in 31.3.3 Results Validation—Once a standard or sample has
Appendix X2, were used during the analysis. been measured, a procedure should be carried out to validate
that measurement. This requires the operator to check for
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
basis. If drift monitors are used, they shall also be run on a
regular basis. The tolerance levels of the checks made using
these monitors should be such that a protocol of either drift
correction or total recalibration is carried out if the results fall
outside these levels. All measurements should be repeated
between the last accepted monitor result and point of non{
compliance should a current monitor measurement prove to be
outside acceptable levels.
32. Precision and Bias8

32.1 Precision—The precision of these procedures as deter-
mined by the statistical examination of the interlaboratory test
results is provided below. The precision statements were
determined on samples analyzed by Procedures A, B, and C as
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,
FIG. 1 Recovery of Organic Chloride Spikes and RR:D02-1875 for Procedure C.
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12
D4929 − 17
written. When method modification is employed, such as that TABLE 3 Calculated Precision Values, Procedure C XRF
described in Appendix X2, the published precision may not Cl, Repeatability r, mg/kgA Reproducibility R, mg/kgB
apply. mg/kg MWDXRF MEDXRF EDXRF MWDXRF MEDXRF EDXRF
1 0.6 0.6 1.1 1.2 1.5 2.4
32.1.1 Repeatability—The difference between successive 2 0.9 0.8 1.4 1.7 2.0 3.0
results obtained by the same operator with the same apparatus 3 1.0 1.0 1.7 2.0 2.4 3.6
under constant operating conditions on identical test materials 4 1.2 1.1 1.9 2.3 2.8 4.1
5 1.3 1.2 2.1 2.5 3.0 4.5
would, in the long run, in the normal and correct operation, 6 1.4 1.3 2.3 2.7 3.3 4.9
exceed the following values only in one case in twenty. 8 1.6 1.5 2.6 3.1 3.7 5.6
32.1.1.1 Procedure A—Values can be obtained for 10 1.8 1.6 2.9 3.4 4.1 6.2
12 1.9 1.8 3.1 3.7 4.5 6.7
organically-bound chlorine for any given concentration above A
Values calculated from Eq 19 for MWDXRF, Eq 20 for MEDXRF, and Eq 21 for
1 µg ⁄g Cl (in the original crude oil specimen) as follows: EDXRF.
B
r 5 0.32 ~ X10.33! 0.644 (17) Values calculated from Eq 22 for MWDXRF, Eq 23 for MEDXRF, and Eq 24 for
EDXRF.
where:
X = µg/g chloride.
32.1.1.2 Procedure B—Values can be obtained for where:
organically-bound chlorine for any given concentration above X = µg/g chloride.
1 µg ⁄g Cl (in the original crude oil specimen) as follows: 32.1.2.2 Procedure B—Values can be obtained for
r 5 1.01 ~ X 2 0.17! 0.467 (18) organically-bound chlorine for any given concentration above
1 µg ⁄g Cl (in the original crude oil specimen) as follows:
where:
X = µg/g chloride. R 5 1.32 ~ X 2 0.17! 0.467 (26)
32.1.1.3 Procedure C—Values can be obtained for where:

organically-bound chlorine for any given concentration above X = µg/g chloride.
1 mg/kg Cl (in the original crude oil specimen) as specified in 32.1.2.3 Procedure C—Values can be obtained for
Table 2. See Table 3 for calculated values. See Note 8 for organically-bound chlorine for any given concentration above
details of the ILS. 1 mg/kg Cl (in the original crude oil specimen) as specified in
32.1.2 Reproducibility—The difference between two single Table 2. See Table 3 for calculated values. See Note 8 for
and independent results obtained by different operators work- details of the ILS.
ing in different laboratories on identical material would, in the 32.1.3 Procedure C—Between{Method Relative Bias can be
long run, exceed the following values only in one case in expressed as follows:
twenty. 32.1.3.1 Degree of Agreement between results by MEDXRF
32.1.2.1 Procedure A—Values can be obtained for and MWDXRF—Results on the same materials produced by
organically-bound chlorine for any given concentration above MEDXRF and MWDXRF have been assessed in accordance
1 µg ⁄g Cl (in the original crude oil specimen) as follows: with procedures outlined in Practice D6708. The findings are
R 5 0.7 ~ X10.33! 0.644 (25) that the degree of agreement between results from MEDXRF
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
TABLE 2 Precision Equations, Procedure C XRF in the scope of this method.
Repeatability r, mg/kgA 32.1.3.2 Degree of Agreement between results by EDXRF
MWDXRF
r 5 0.643*X 0.44 (19)
and MEDXRF—Results on the same materials produced by
MEDXRF and MWDXRF have been assessed in accordance
MEDXRF
r 5 0.591*X 0.44 (20)
with procedures outlined in Practice D6708. The findings are
that the degree of agreement between results from EDXRF and
EDXRF
r 5 0.934s X 1 0.4d 0.48 (21)
TABLE 4 Procedure C Between-Method Bias Outcome
Reproducibility R, mg/kgA
MWDXRF Method X Method Y Suggested Bias
R 5 1.235*X 0.44 (22)
CorrectionA
MEDXRF MWDXRF
MEDXRF Ŷ 5 X 2 0.658 (27)
R 5 1.500*X 0.44 (23)
EDXRFB EDXRF MEDXRF

R 5 2.000s X 1 0.4d 0.48 (24) Ŷ 5 X 2 0.519 (28)
A
Where X = mg/kg chloride
B EDXRF MWDXRF No bias correction
The degrees of freedom associated with the reproducibility estimate from this
A
round robin study are 29. Since the minimum requirement of 30 (in accordance Where:
with Practice D6300) is not met, users are cautioned that the actual reproducibility Ŷ = predicted Y-method value
may be significantly different than these estimates. X = single X-method measured results
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13
D4929 − 17
MEDXRF, can be further improved by applying Eq 28 listed in and six EDXRF analyzers. Practice D6300 was followed for the analysis
Table 4. No sample{specific bias, as defined in Practice D6708, of data. The data would not support a pooled precision statement, so
separate precisions were determined for each XRF technique. See RR
was observed after the bias{correction for the materials in the D02:1875 for details of this study.
scope of this method.
32.1.3.3 Degree of Agreement between results by EDXRF 32.2 Bias—The bias for either Procedure A or B has been
and MWDXRF—Results on the same materials produced by demonstrated by performing analyses using known spiked
EDXRF and MWDXRF have been assessed in accordance with concentrations of various organic chloride compounds in a
procedures outlined in Practice D6708. The findings are that no variety of crude oils to be lower than the true value. This is
bias{correction considered in Practice D6708 can further im- because not all of the volatile components will distill from a
prove the agreement between results from EDXRF and complex crude oil under the conditions of this test method. The
MWDXRF for the materials studied. No sample{specific bias, extent of this bias is shown in Fig. 1, where various recoveries
as defined in Practice D6708, was observed for the materials in are shown plotted against the known concentration of pure
the scope of this method. organic-chloride compound spikes.
32.2.1 See Fig. 2 for a recovery plot of Procedure C.
NOTE 8—Procedure C Interlaboratory Study—Eight participants dis-
tilled ten crude samples in blind duplicate and performed washes on the 33. Keywords
twenty naphtha fractions. Six of the eight participants measured each
washed naphtha fraction by monochromatic wavelength dispersive XRF 33.1 chlorine; coulometry; crude oil; EDXRF; Energy Dis-
(MWDXRF), monochromatic energy dispersive XRF (MEDXRF), and persive X-ray Fluorescence; MEDXRF; Monochromatic En-
energy dispersive XRF (EDXRF) (three measurements per naphtha ergy Dispersive X-ray Fluorescence; Monochromatic Wave-
sample). One participant measured each washed naphtha fraction by length Dispersive X-ray Fluorescence; Monochromatic X-ray;
MWDXRF and MEDXRF, and one participant measured each washed
naphtha fraction once by MWDXRF and twice by MEDXRF using two MWDXRF; naphtha; organic chloride; organo-chlorine; polar-
MEDXRF analyzers manufactured by two vendors. The participant total ization; sodium biphenyl; spectrometry; X-ray; X-ray Fluores-
by technology was eight MWDXRF analyzers, nine MEDXRF analyzers, cence; XRF
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14
D4929 − 17
FIG. 2 Average Recovery of Organic Chloride Spikes by XRF
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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.

15
D4929 − 17
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 – 16) that may impact the use of this standard. (Approved Oct. 15, 2017.)
(1) Revised subsections 1.1, 3.2, and 11.2. (9) Renumbered old Equations 10, 11, 12, 13 to 17, 18, 25, 26.
(2) Renumbered old subsections 1.5, 1.6 to 1.6.1, 1.7. (10) Renumbered old Section 23 to new Section 30 and revised
(3) Added new subsections 1.5, 3.2.6, 5.3, 5.3.1, 5.3.2, 5.3.3, sections 30.1, 30.2, and 30.3.
5.3.4, and 5.3.5. (11) Renumbered old Section 24 to new Section 31 and added
(4) Added three practices to subsection 2.1. subsections 31.3, 31.3.1, 31.3.1.1, 31.3.2, 31.3.3, 31.3.4,
(5) Added Procedure C—X-ray Fluorescence Spectrometry 31.3.5, and 31.3.6.
Sections 23, 24, 25, 26, 27, 28, 29, 30 (12) Renumbered old Section 25 to 32, revised subsection 32.1,
(6) Added Notes 3-8. and added subsections 32.1.1.3, 32.1.2.3, 32.1.3, 32.1.3.1,
(7) Added Tables 1-4. 32.1.3.2, 32.1.3.3, and 32.2.1.
(8) Added Equations 10, 11, 12, 13, 14, 15, 16, 19, 20, 21, 22, (13) Added Fig. 2.
23, and 24. (14) Renumbered Sections 26 to 33 and added 14 keywords.
(D4929 – 15a) that may impact the use of this standard. (Approved Oct. 1, 2016.)
(1) Revised subsection 32.1. (3) Changed the title of the two methods within the standard to
(2) Added new subsection 30.3 and Appendix X2. Procedure A and Procedure B, throughout.
(D4929 – 15) that may impact the use of this standard. (Approved Dec. 1, 2015.)
(1) Revised subsections 4.1, 4.1.1, 4.1.2, 4.1.2.1, 4.1.3, and (2) Added new subsection 4.1.1.1.
4.2.
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16
D4929 − 17
(D4929 – 07 (2014)) that may impact the use of this standard. (Approved June 1, 2015.)
(1) Added information in new subsections 4.1 and 4.2. (2) Added a new Report Section 30.
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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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make your views known to the ASTM Committee on Standards, at the address shown below.
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This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
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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* 2. Referenced Documents

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

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used for daily monitoring of drift.

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in commercially available transparent films and vary from lot

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trichlorobenzene, samples on a given day, analyze the drift correction monitor(s)

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32. Precision and Bias8

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32.1.1.3 Procedure C—Values can be obtained for where:

EDXRFB EDXRF MEDXRF

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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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