Designation: D5194 − 13

Standard Test Method for

Trace Chloride in Liquid Aromatic Hydrocarbons1
This standard is issued under the fixed designation D5194; 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* D3437 Practice for Sampling and Handling Liquid Cyclic

1.1 This test method covers the determination of total Products
chloride (organic and inorganic) in liquid aromatic hydrocar- D3505 Test Method for Density or Relative Density of Pure
bons and cyclohexane. Liquid Chemicals
D4052 Test Method for Density, Relative Density, and API
1.2 The test method is applicable to samples with chloride Gravity of Liquids by Digital Density Meter
concentrations of 1 to 25 mg/kg. D6809 Guide for Quality Control and Quality Assurance
1.3 Bromides and iodides, if present, will be calculated as Procedures for Aromatic Hydrocarbons and Related Ma-
chlorides. terials
1.4 Materials, such as styrene, that are polymerized by E29 Practice for Using Significant Digits in Test Data to
sodium biphenyl reagent cannot be analyzed by this test Determine Conformance with Specifications
method. 2.2 Other Documents:3
1.5 In determining the conformance of the test results using OSHA Regulations, 29 CFR paragraphs 1910.1000 and
this method to applicable specifications, results shall be 1910.1200
rounded off in accordance with the rounding-off method of
Practice E29. 3. Summary of Test Method

1.6 The values stated in SI units are to be regarded as 3.1 A known amount of hydrocarbon sample is transferred
standard. No other units of measurement are included in this into a separatory funnel containing toluene. Sodium biphenyl
standard. reagent is added to convert organic halogens into inorganic
halides. The excess reagent is decomposed with water and the
1.7 This standard does not purport to address all of the phases are separated. The aqueous phase is acidified, washed,
safety concerns, if any, associated with its use. It is the and concentrated. Acetone is added and the solution is titrated
responsibility of the user of this standard to establish appro- with silver nitrate solution.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. For a specific 4. Significance and Use
hazard statement, see Section 7.
4.1 Organic and inorganic chlorine compounds can have a
2. Referenced Documents deleterious effect on equipment and reactions in processes
2.1 ASTM Standards:2 involving aromatic hydrocarbons.
D891 Test Methods for Specific Gravity, Apparent, of Liquid 4.2 Maximum chloride levels are often specified for process
Industrial Chemicals streams and for aromatic hydrocarbon products.
D1193 Specification for Reagent Water
D1555M Test Method for Calculation of Volume and Weight 5. Apparatus
of Industrial Aromatic Hydrocarbons and Cyclohexane
5.1 Titrator, potentiometric, recording, + 2000 mV range, 1
[Metric]
mV resolution with dispenser having a volume readout of 0.00
1
to 9.99 mL or 0.00 to 99.99 mL and 0.01 % resolution.
This test method is under the jurisdiction of ASTM Committee D16 on
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of 5.2 Electrode, glass, reference.
Subcommittee D16.04 on Instrumental Analysis.
Current edition approved July 1, 2013. Published July 2013. Originally approved 5.3 Electrode, silver, billet type.
in 1991. Last previous edition approved in 2011 as D5194 – 11a. DOI: 10.1520/
D5194-13.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
3
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM Available from U.S. Government Printing Office Superintendent of Documents,
Standards volume information, refer to the standard’s Document Summary page on 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http://
the ASTM website. www.access.gpo.gov.

*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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 D5194 − 13
6. Reagents and Materials 7. Hazards
6.1 Purity of Reagents—Reagent grade chemicals shall be 7.1 A material, such as styrene, which is polymerized by
used in all tests. Unless otherwise indicated, it is intended that sodium biphenyl can cause a violent reaction and should never
all reagents conform to the specifications of the Committee on be used as the sample.
Analytical Reagents of the American Chemical Society, where 7.2 Consult current OSHA regulations and suppliers’ Mate-
such specifications are available.4 Other grades may be used, rial Safety Data Sheets, and local regulations for all materials
provided it is first ascertained that the reagent is of sufficiently used in this test method.
high purity to permit its use without lessening the accuracy of
the determination. 8. Sampling
6.2 Purity of Water—Unless otherwise indicated, references 8.1 Refer to Practice D3437 for proper sampling and han-
to water shall be understood to mean reagent water as defined dling of liquid hydrocarbons analyzed by this test method.
by Types II or III of Specification D1193.
9. Electrode Preparation
6.3 Acetone, 99.9 % purity.
9.1 Clean the surface of the silver electrode with mild
6.4 Congo Red Paper. detergent and scouring powder, and rinse with water.
6.5 Detergent, residue free. 9.2 Immerse the electrode in the saturated potassium chlo-
6.6 Isobutanol, 99.9 % minimum purity. ride solution until the electrode tip turns light gray.
9.3 Rinse well with water and attach to the titrimeter.
6.7 Isooctane.
9.4 Repeat the electrode preparation when the silver chlo-
6.8 Nitric Acid, concentrated.
ride film begins to peel from the surface, or if the film becomes
6.9 Nitric Acid, 5-M. Dilute 160 mL concentrated nitric acid discolored.
to 500 mL with water.
10. Procedure for Total Chloride
6.10 Potassium Chloride, primary standard.
10.1 Extreme care must be used to prevent contamination
6.11 Potassium Chloride Solution, saturated. and all glassware should be exclusively reserved for this
6.12 Scouring Powder, cleanser. analysis. Just prior to use, the glassware should be rinsed with
water followed by acetone and then air dried.
6.13 Silver Nitrate, 99.99 % minimum purity.
10.2 Place 50 mL of toluene into a 250-mL separatory
6.14 Silver Nitrate Solution, 0.01 N, standardized to 0.1 %. funnel and pipet in the amount of the liquid sample that
NOTE 1—This solution may be obtained as follows: corresponds to the estimated chloride content as prescribed in
(1) Purchase from a laboratory supply company, (2) Weigh to four Table 1.
places, 1.680 to 1.720 g silver nitrate, transfer quantitatively into a
1000-mL volumetric flask, make to mark with water, and mix well. NOTE 2—It is generally more convenient to measure the liquid samples
by volume and then convert to mass using density or relative density.
Weight AgNO3 Table 2 lists the relative densities of several pure hydrocarbons. Densities
Normality of solution 5 of unknowns may be determined by using Test Methods D891, D3505 or
169.9
or (3) Dissolve 8.5 g silver nitrate in 500 mL water to give a 0.1 N D4052.
solution. Weigh 0.09 to 0.10 g of dried (105°C) potassium chloride to NOTE 3—Alternately, place the sample into a 125-mL bottle and weigh.
the nearest 0.1 mg into a 250-mL electrolytic beaker, add 100 mL of From the contents of this bottle add the appropriate amount of the sample
to the toluene in the separatory funnel. Reweigh the bottle, and determine
water and a stirring bar. While stirring, titrate with the silver nitrate
the weight of the analytical specimen.
solution.
10.3 Add the contents of one vial of sodium biphenyl
Weight KCl
Normality of AgNO3 solution 5 reagent, stopper the separatory funnel, and gently swirl to mix
0.0746 3 mL AgNO3
Pipet 50.00 mL of the solution into a 500-mL volumetric flask, dilute to thoroughly, venting the funnel from time to time. If the
mark with water, and mix well. Divide the calculated normality of the resulting solution or suspension is not blue-green, add more
0.1 N solution by 10 to give the normality of final AgNO3 solution. sodium biphenyl reagent (one vial at a time) until the blue
green color persists.
6.15 Sodium Biphenyl Reagent—The reagent is normally
packed in individual vials that contain 0.2 to 0.4 g of active NOTE 4—The sodium biphenyl reagent has a limited shelf life, given as
sodium each. six months by the manufacturer. This can be extended, in most cases, to
approximately one year by keeping the reagent under refrigeration. If this
6.16 Toluene, 99.9 % minimum purity. is done, the reagent should be kept at room temperature for several days
just prior to use to dissolve any sodium biphenyl that may have
precipitated upon cooling.

4
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not TABLE 1 Specimen Size
listed by the American Chemical Society, see Analar Standards for Laboratory Estimated chloride, mg/kg Specimen volume, mL
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia 0 to 5 100
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 5 to 25 50
MD.

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 D5194 − 13
TABLE 2 Densities of Hydrocarbons 35,500 ~ A 2 B !
Chloride, mg/kg 5 N (1)
Component Density in vacuo VD
at 20°C
g/cc where:
Benzene 0.87908 A = volume of titrant for aqueous phase, mL,
Cyclohexane 0.77849
Ethylbenzene 0.86685
B = volume of titrant for blank, mL,
Isopropylbenzene (cumene) 0.86160 N = normality of silver nitrate solution,
Styrene 0.90586 V = volume of sample, mL, and
Toluene 0.86686 D = density or relative density of sample.
m-Xylene 0.86408
o-Xylene 0.87968 13.2 Calculate organic chloride as follows:
p-Xylene 0.86076
Organic chloride, mg/kg 5 T 2 I (2)

where:
10.4 Allow the mixture to stand for approximately 10 min.
Slowly add 20 mL water and swirl gently with the funnel T = total chloride, mg/kg and
unstoppered until the blue-green color changes to white. I = inorganic chloride, mg/kg.
Stopper the funnel again and rock it gently for 1 min, venting 13.3 Report chloride to the nearest 0.1 mg/kg.
the pressure frequently through the stopcock.
14. Precision and Bias
10.5 Add 10 mL 5 N nitric acid, and then 5 mL isobutanol.
Shake gently, releasing the pressure frequently through the 14.1 Precision:
stopcock. 14.1.1 The data for determining the precision of this test
method are based on the analyses of toluene, ethylbenzene, and
10.6 Drain the aqueous phase into another 250-mL separa-
p-xylene that had been spiked with organic chloride com-
tory funnel containing 50 mL isooctane and shake well. Drain
pounds to the 1, 5, and 25 mg/kg chloride levels each.
the aqueous phase into a 250-mL electrolytic beaker.
14.1.2 The following criteria should be used to judge the
10.7 Make a second extraction of the specimen solution acceptability (95 % probability) of results obtained by this test
with 20 mL water acidified with 6 drops of 5-M nitric acid and method. The criteria were derived from a round robin between
drain the aqueous phase into the separatory funnel containing three laboratories. Each sample was run on two different days
the isooctane. After shaking, allow the phases to separate and in each laboratory.
drain the aqueous phase into the beaker containing the first 14.1.2.1 Intermediate Precision (formerly called
water extract. Repeatability)—Results in the same laboratory should not be
10.8 Test the aqueous solution with Congo red paper, and if considered suspect unless they differ by more than 0.5 mg/kg.
it does not test acidic, add 5-N nitric acid dropwise with stirring 14.1.2.2 Reproducibility—Results from each of two labora-
until the test paper turns dark blue. tories should not be considered suspect unless they differ by
more than 0.9 mg/kg.
10.9 Evaporate the solution to about 30 mL on a hot plate.
10.9.1 Warning: Loss of chloride may result if the solution 14.2 Bias—The bias of this test method cannot be deter-
is boiled or evaporated below 25 mL. mined because no referee method is available to determine the
true value.
10.10 Allow the solution to cool, and add 100 mL of
acetone. Titrate the solution potentiometrically with standard
15. Quality Guidelines
0.01 N silver nitrate solution and determine the volume of
titrant used to reach the end point. 15.1 Laboratories shall have a quality control system in
place.
10.11 Determine a blank for each group of samples, using
15.1.1 Confirm the performance of the test instrument or
all the reagents including as many vials of sodium biphenyl as
test method by analyzing a quality control sample following
were used in the analysis of a sample. Follow all the operations
the guidelines of standard statistical quality control practices.
of the analysis, except omit the specimen itself.
15.1.2 A quality control sample is a stable material isolated
11. Procedure for Inorganic Chloride from the production process and representative of the sample
being analyzed.
11.1 Follow the procedure in Section 10 but without adding
15.1.3 When QA/QC protocols are already established in
the sodium biphenyl reagent to either the sample or the blank.
the testing facility, these protocols are acceptable when they
12. Procedure for Organic Chloride confirm the validity of test results.
12.1 Follow the procedures given in Sections 10 and 11 to 15.1.4 When there are no QA/QC protocols established in
determine the total and inorganic chlorides. Subtract the the testing facility, use the guidelines described in Guide
inorganic from the total chloride to give the organic chloride. D6809 or similar statistical quality control practices.

13. Calculation 16. Keywords

13.1 Calculate either the total or inorganic chloride as 16.1 aromatic hydrocarbons; chloride; cyclohexane; ethyl-
follows: benzene; p-xylene; toluene

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 D5194 − 13

SUMMARY OF CHANGES

Committee D16 has identified the location of selected changes to this standard since the last issue (D5194-11a)
that may impact the use of this standard. (Approved July 1, 2013.)

(1) Updated Section 6.15 to reflect multiple size vials available

for reagent.

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