ASTM D5194-24

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it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D5194 − 18 D5194 − 24
Standard Test Method for
Trace Chloride in Liquid Aromatic Hydrocarbons
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*
1.1 This test method covers the determination of total chloride (organic and inorganic) in liquid aromatic hydrocarbons and
cyclohexane.
1.2 The test method is applicable to samples with chloride concentrations of 11 mg ⁄kg to 25 mg/kg.
1.3 Bromides and iodides, if present, will be calculated as chlorides.
1.4 Materials, such as styrene, that are polymerized by sodium biphenyl reagent cannot be analyzed by this test method.
1.5 In determining the conformance of the test results using this method to applicable specifications, results shall be rounded off
in accordance with the rounding-off method of Practice E29.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of
regulatory limitations prior to use. For a specific hazard statement, see Section 7.
1.8 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.
2. Referenced Documents
2.1 ASTM Standards:
D891 Test Methods for Specific Gravity, Apparent, of Liquid Industrial Chemicals
D1193 Specification for Reagent Water
D1555M Test Method for Calculation of Volume and Weight of Industrial Aromatic Hydrocarbons and Cyclohexane [Metric]
D3437 Practice for Sampling and Handling Liquid Cyclic Products
D3505 Test Method for Density or Relative Density of Pure Liquid Chemicals (Withdrawn 2023)
D4052 Test Method for Density, Relative Density, and API Gravity of Liquids by Digital Density Meter
This test method is under the jurisdiction of ASTM Committee D16 on Aromatic, Industrial, Specialty and Related Chemicals and is the direct responsibility of
Subcommittee D16.04 on Instrumental Analysis.
Current edition approved Jan. 1, 2018Jan. 1, 2024. Published January 2018January 2024. Originally approved in 1991. Last previous edition approved in 20132018 as
D5194 – 13.D5194 – 18. DOI: 10.1520/D5194-18.10.1520/D5194-24.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
*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
D5194 − 24
D6809 Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
E29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
2.2 Other Documents:
OSHA Regulations, 29 CFR paragraphs 1910.1000 and 1910.1200
3. Summary of Test Method
3.1 A known amount of hydrocarbon sample is transferred into a separatory funnel containing toluene. Sodium biphenyl reagent
is added to convert organic halogens into inorganic halides. The excess reagent is decomposed with water and the phases are
separated. The aqueous phase is acidified, washed, and concentrated. Acetone is added and the solution is titrated with silver nitrate
solution.
4. Significance and Use
4.1 Organic and inorganic chlorine compounds can have a deleterious effect on equipment and reactions in processes involving
aromatic hydrocarbons.
4.2 Maximum chloride levels are often specified for process streams and for aromatic hydrocarbon products.
5. Apparatus
5.1 Titrator, potentiometric, recording, + 2000 mV range, 1 mV resolution with dispenser having a volume readout of 0.000.00 mL
to 9.99 mL or 0.000.00 mL to 99.99 mL and 0.01 % resolution.
5.2 Electrode, glass, reference.
5.3 Electrode, silver, billet type.
6. Reagents and Materials
6.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such
specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
6.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water as defined by
Types II or III of Specification D1193.
6.3 Acetone, 99.9 % purity.
6.4 Congo Red Paper.
6.5 Detergent, residue free.
6.6 Isobutanol, 99.9 % minimum purity.
6.7 Isooctane.
Available from U.S. Government Printing Office Superintendent of Documents, 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http://
www.access.gpo.gov.
Reagent Chemicals, American Chemical Society Specifications,ACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference
Materials, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for
Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC),
Rockville, MD.
D5194 − 24
6.8 Nitric Acid, concentrated.
6.9 Nitric Acid, 5-M. Dilute 160 mL concentrated nitric acid to 500 mL with water.
6.10 Potassium Chloride, primary standard.
6.11 Potassium Chloride Solution, saturated.
6.12 Scouring Powder, cleanser.
6.13 Silver Nitrate, 99.99 % minimum purity.
6.14 Silver Nitrate Solution, 0.01 N, standardized to 0.1 %.
NOTE 1—This solution may be obtained as follows:
(1) Purchase from a laboratory supply company, (2) Weigh to four places, 1.6801.680 g to 1.720 g silver nitrate, transfer quantitatively into a
1000-mL1000 mL volumetric flask, make to mark with water, and mix well.
Weight AgNO
Normality of solution 5
169.9
or (3) Dissolve 8.5 g silver nitrate in 500 mL 500 mL water to give a 0.1 N solution. Weigh 0.090.09 g to 0.10 g of dried (105°C)(105 °C) potas-
sium chloride to the nearest 0.1 mg into a 250-mL250 mL electrolytic beaker, add 100 mL of water and a stirring bar. While stirring, titrate with the
silver nitrate solution.
Weight KCl
Normality of AgNO solution 5
0.0746 ×mL AgNO
Pipet 50.00 mL of the solution into a 500-mL500 mL volumetric flask, dilute to mark with water, and mix well. Divide the calculated normality of
the 0.1 N solution by 10 to give the normality of final AgNO solution.
6.15 Sodium Biphenyl Reagent—The reagent is normally packed in individual vials that contain 0.2 to 0.4 g 0.2 g to 0.4 g of active
sodium each.
6.16 Toluene, 99.9 % minimum purity.
7. Hazards
7.1 A material, such as styrene, which is polymerized by sodium biphenyl can cause a violent reaction and should never be used
as the sample.
7.2 Consult current OSHA regulations and suppliers’ Safety Data Sheets, and local regulations for all materials used in this test
method.
8. Sampling
8.1 Refer to Practice D3437 for proper sampling and handling of liquid hydrocarbons analyzed by this test method.
9. Electrode Preparation
9.1 Clean the surface of the silver electrode with mild detergent and scouring powder, and rinse with water.
TABLE 1 Specimen Size
Estimated chloride, mg/kg Specimen volume, mL
0 to 5 100
5 to 25 50
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TABLE 2 Densities of Hydrocarbons
Density in vacuo
Component at 20°C20 °C
g/cc
Benzene 0.87908
Cyclohexane 0.77849
Ethylbenzene 0.86685
Isopropylbenzene (cumene) 0.86160
Styrene 0.90586
Toluene 0.86686
m-Xylene 0.86408
o-Xylene 0.87968
p-Xylene 0
...