ASTM D4423-23

Standard Test Method for Determination of Carbonyls in C<inf>4</inf> Hydrocarbons

SIGNIFICANCE AND USE
4.1 The determination of the carbonyl content of polymerization-grade 1,3-butadiene is necessary, since in some polymerization reactions, the presence of carbonyls in excess over some specified amount can have a deleterious effect upon the polymer properties or the reaction itself, or both.
SCOPE
1.1 This test method covers the determination of carbonyls (ketones and aldehydes) in C4 hydrocarbons. This test method was tested on polymerization-grade 1,3-butadiene.  
1.2 The applicable range for this test method is 0 mg/kg to 50 mg/kg carbonyls calculated as acetaldehyde.  
1.3 Other C4 hydrocarbons and their mixtures besides polymerization-grade 1,3-butadiene could be tested using this same test method. However, the precision section of this test method covers only carbonyls in applicable range as listed in 1.2, as found in polymerization-grade 1,3-butadiene.  
1.4 WARNING—Mercury has been designated by many regulatory agencies as a hazardous substance that can cause serious medical issues. Mercury, or its vapor, has been demonstrated to be hazardous to health and corrosive to materials. Use caution when handling mercury and mercury-containing products. See the applicable product Safety Data Sheet (SDS) for additional information. The potential exists that selling mercury or mercury-containing products, or both, is prohibited by local or national law. Users must determine legality of sales in their location.  
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.6.1 The user is advised to obtain LPG safety training for the safe operation of this test method procedure and related activities.  
1.7 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.

General Information

• Status: Published
• Publication Date: 28-Feb-2023
• ICS: 71.080.80 - Aldehydes and ketones
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.D0.04 - C4 and C5 Hydrocarbons

Relations

• Refers: ASTM E1-13 - Standard Specification for ASTM&ensp;Liquid-in-Glass Thermometers
• Effective Date: 01-May-2013
• Refers: ASTM E1-07 - Standard Specification for ASTM Liquid-in-Glass Thermometers
• Effective Date: 01-Nov-2007
• Refers: ASTM D1193-06 - Standard Specification for Reagent Water
• Effective Date: 01-Mar-2006
• Refers: ASTM E1-05 - Standard Specification for ASTM Liquid-in-Glass Thermometers
• Effective Date: 01-Nov-2005
• Refers: ASTM E1-03a - Standard Specification for ASTM Liquid-in-Glass Thermometers
• Effective Date: 01-Nov-2003
• Refers: ASTM E1-03 - Standard Specification for ASTM Thermometers
• Effective Date: 10-May-2003
• Refers: ASTM E1-01 - Standard Specification for ASTM Thermometers
• Effective Date: 10-Oct-2001
• Refers: ASTM E1-98e1 - Standard Specification for ASTM Thermometers
• Effective Date: 10-Oct-2001
• Refers: ASTM E1-98 - Standard Specification for ASTM Thermometers
• Effective Date: 10-Oct-2001
• Refers: ASTM D1193-99e1 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999
• Refers: ASTM D1193-99 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999

Overview

ASTM D4423-23, titled Standard Test Method for Determination of Carbonyls in C₄ Hydrocarbons, establishes a reliable procedure for quantifying carbonyl compounds (ketones and aldehydes) in C₄ hydrocarbons, most notably in polymerization-grade 1,3-butadiene. Excessive carbonyl content can negatively impact polymerization reactions and the quality of the resulting polymers. This standard is essential for ensuring that carbonyl levels are within acceptable limits, supporting both process efficiency and product integrity in industries that rely on high-purity C₄ hydrocarbon feedstocks.

Key Topics

• Scope and Applicability
  • Applies to the analysis of carbonyls in C₄ hydrocarbons, with proven performance for polymerization-grade 1,3-butadiene.
  • Applicable concentration range: 0 mg/kg to 50 mg/kg, reported as acetaldehyde.
  • May be suitable for other C₄ hydrocarbon mixtures, though precision is validated only for 1,3-butadiene within the stated range.
• Significance of Carbonyl Determination
  • Even trace levels of carbonyls can alter polymerization efficiency and final product properties.
  • Strict monitoring helps prevent defects or undesired reactions in polymer production.
• Test Method Summary
  • The method involves titrating a sample with alcoholic solutions of hydroxylamine hydrochloride and potassium hydroxide, using colorimetric detection and careful blank adjustments.
  • Results are expressed in mg/kg of carbonyls, calculated as acetaldehyde.
• Safety Considerations
  • Use of hazardous reagents, including mercury (where applicable), requires adherence to safety data sheets and regulatory compliance.
  • Laboratory personnel should have liquid petroleum gas (LPG) safety training for secure method execution.
• Units and International Harmonization
  • All measurements are reported in SI units.
  • Developed in alignment with globally recognized standardization principles, supporting regulatory compliance across markets.

Applications

• Quality Control in Polymer Production
  • Direct use by manufacturers of synthetic rubber and plastics to monitor and control carbonyl impurities in 1,3-butadiene.
• Hydrocarbon Feedstock Assessment
  • Suitable for evaluating the purity of various C₄ hydrocarbons used in downstream chemical processing and industrial synthesis.
• Lab Analysis and Certification
  • Utilized by testing laboratories and quality assurance teams to certify hydrocarbon streams, ensuring compliance with customer or regulatory specifications.
• Research and Development
  • Applicable in R&D settings focused on optimizing hydrocarbon processing, improving catalyst performance, or studying effects of carbonyl contaminants on polymer properties.

Related Standards

For broader context and effective laboratory practice, the following ASTM standards are frequently referenced alongside ASTM D4423-23:

• ASTM D1193 - Specification for Reagent Water
• ASTM E1 - Specification for ASTM Liquid-in-Glass Thermometers
• ASTM D484 - Specification for Hydrocarbon Dry Cleaning Solvents (for historical reference)

These supporting standards help laboratories maintain appropriate reagent and equipment quality, ensuring accurate and reliable results in carbonyl analysis of C₄ hydrocarbons.

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Keywords: ASTM D4423-23, carbonyl determination, C4 hydrocarbons, 1,3-butadiene, polymerization-grade hydrocarbons, acetaldehyde, chemical analysis, hydrocarbon purity, polymer quality control, titration method, industrial standards compliance

Standards Content (Sample)

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: D4423 − 23
Standard Test Method for
Determination of Carbonyls in C Hydrocarbons
This standard is issued under the fixed designation D4423; 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* Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
1.1 This test method covers the determination of carbonyls
Barriers to Trade (TBT) Committee.
(ketones and aldehydes) in C hydrocarbons. This test method
was tested on polymerization-grade 1,3-butadiene.
2. Referenced Documents
1.2 The applicable range for this test method is 0 mg ⁄kg to 2
2.1 ASTM Standards:
50 mg ⁄kg carbonyls calculated as acetaldehyde.
D484 Specification for Hydrocarbon Dry Cleaning Solvents
1.3 Other C hydrocarbons and their mixtures besides
(Withdrawn 1982)
polymerization-grade 1,3-butadiene could be tested using this
D1193 Specification for Reagent Water
same test method. However, the precision section of this test
E1 Specification for ASTM Liquid-in-Glass Thermometers
method covers only carbonyls in applicable range as listed in
3. Summary of Test Method
1.2, as found in polymerization-grade 1,3-butadiene.
3.1 A measured amount of sample is added to an alcoholic
1.4 WARNING—Mercury has been designated by many
hydroxylamine hydrochloride solution that has been adjusted
regulatory agencies as a hazardous substance that can cause
to a given coloration using either alcoholic acid or base. The
serious medical issues. Mercury, or its vapor, has been dem-
carbonyls will react with the hydroxylamine hydrochloride
onstrated to be hazardous to health and corrosive to materials.
releasing an equivalent amount of hydrochloric acid which is
Use caution when handling mercury and mercury-containing
then back-titrated to the original coloration. A blank containing
products. See the applicable product Safety Data Sheet (SDS)
only methanol and sample is titrated and the sample’s results
for additional information. The potential exists that selling
are calculated using the blank adjustment. Results are reported
mercury or mercury-containing products, or both, is prohibited
as milligrams per kilogram carbonyls as acetaldehyde.
by local or national law. Users must determine legality of sales
in their location.
4. Significance and Use
1.5 The values stated in SI units are to be regarded as
4.1 The determination of the carbonyl content of
standard. No other units of measurement are included in this
polymerization-grade 1,3-butadiene is necessary, since in some
standard.
polymerization reactions, the presence of carbonyls in excess
1.6 This standard does not purport to address all of the
over some specified amount can have a deleterious effect upon
safety concerns, if any, associated with its use. It is the
the polymer properties or the reaction itself, or both.
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter- 5. Apparatus
mine the applicability of regulatory limitations prior to use.
5.1 Bunsen Valves—A device constructed so that when used
1.6.1 The user is advised to obtain LPG safety training for
with an Erlenmeyer flask, the sample vapors can exit the flask
the safe operation of this test method procedure and related
while protecting the flask’s liquid contents. See Fig. 1 for
activities.
details.
1.7 This international standard was developed in accor-
5.2 Cooling Coil—Prepare a cooling coil by winding about
dance with internationally recognized principles on standard-
10 cm to 15 cm of seamless copper tubing (about 6 mm
ization established in the Decision on Principles for the
diameter) on a short length of pipe (about 1.5 cm to 2.0 cm
1 2
This test method is under the jurisdiction of ASTM Committee D02 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Subcommittee D02.D0.04 on C4 and C5 Hydrocarbons. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved March 1, 2023. Published June 2023. Originally the ASTM website.
approved in 1984. Last previous edition approved in 2015 as D4423 – 10 (2015). The last approved version of this historical standard is referenced on
DOI: 10.1520/D4423-23. 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
D4423 − 23
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 Type II reagent water
conforming to Specification D1193.
6.3 Alcoholic Hydrochloric Acid (0.05 N)—Dilute 4.2 mL of
concentrated hydrochloric acid (Warning—Poison. Corrosive.
May be fatal if swallowed. Liquid and vapor cause severe
burns. Harmful if inhaled.) to volume with anhydrous methanol
in a 1 L volumetric flask. Use the alcoholic 0.05 N potassium
hydroxide solution to standardize the HCl solution.
6.4 Alcoholic Hydroxylamine Hydrochloride—Dissolve
FIG. 1 Apparatus
35.0 g of hydroxylamine hydrochloride (Warning—May be
irritating to skin, eyes, or mucous membranes. Harmful if
diameter), allowing sufficient length of tubing at the end of the
inhaled.) in 3.5 L of anhydrous methanol. (Warning—
coil to connect it to the sample source. Attach a valve at a point
Flammable. Vapor harmful. May be fatal or cause blindness if
that would not extend more than 8 cm above the surface of the
swallowed or inhaled. Cannot be made nonpoisonous.)
cooling bath liquid. To the valve, attach a 6 cm to 8 cm length
piece of tubing bent downward so that the hydrocarbon liquid 6.5 Alcoholic Potassium Hydroxide (0.05 N)—Dissolve
can be directed into the receiving container.
3.3 g of potassium hydroxide in anhydrous methanol.
(Warning—Corrosive. Can cause severe burns or blindness.
5.3 Dewar Flask—The Dewar flask must be of sufficient
Evolution of heat produces a violent reaction or eruption upon
volume to completely immerse the main portion of the cooling
too rapid mixture with water.) Make to volume with methanol
coil except for the extremities necessary for receiving and
in a 1 L volumetric flask. Standardize against a primary
delivering the sample through the coil.
standard, potassium acid phthalate.
5.4 Erlenmeyer Flasks, 250 mL capacity.
6.6 Dry Ice (Carbon Dioxide Solid)—(Warning—
5.5 Volumetric Flasks, 1 L capacity. These flasks should be
Extremely cold (−78.5 °C). Liberates heavy gas which may
Class A glassware.
cause suffocation. Contact with skin causes burns or freezing,
5.6 Graduated Cylinders—100 mL capacity, glass or both. Vapors may react violently with hot magnesium or
aluminum alloys.)
cylinders, graduated in 1 mL or 2 mL divisions.
5.7 Microburets, 2.00 mL or 5.00 mL capacity. The mi- 6.7 Stoddard Solvent—Conforming to the specification
croburets should be Class A glassware with 0.01 mL or listed in Specification D484. (Warning—Combustible. Vapor
0.02 mL divisions or less. It is advisable to have the buret’s tip harmful.)
end equipped with a syringe needle to dispense very small
6.8 Thymol Blue Indicator—Dissolve 0.04 g of thymol blue
drops of titrant.
in 100 mL of anhydrous methanol. (Warning—Flammable.
5.8 Sample Cylinders—These should be of sufficient vol- Vapor harmful. May be fatal or cause blindness if swallowed or
ume to give the required amount of sample for testing. inhaled. Cannot be made nonpoisonous.)
Stainless steel cylinders equipped with needle valves should be
7. Preparation of Apparatus
used. It is suggested that a 500 mL-capacity cylinder be the
minimum size to be used for butadiene.
7.1 Dry Ice-Stoddard Solvent Bath— Add a sufficient quan-
tity of Stoddard solvent into the Dewar flask to ensure that the
5.9 Thermometer—For observing temperatures below
−45 °C. The Low Cloud and Pour Point Thermometer, con- cooling co
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D4423 − 10 (Reapproved 2015) D4423 − 23
Standard Test Method for
Determination of Carbonyls in C Hydrocarbons
This standard is issued under the fixed designation D4423; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope Scope*
1.1 This test method covers the determination of carbonyls (ketones and aldehydes) in C hydrocarbons. This test method was
tested on polymerization-grade 1,3-butadiene.
1.2 The applicable range for this test method is 0 mg ⁄kg to 50 mg ⁄kg carbonyls calculated as acetaldehyde.
1.3 Other C hydrocarbons and their mixtures besides polymerization-grade 1,3-butadiene could be tested using this same test
method. However, the precision section of this test method covers only carbonyls in applicable range as listed in 1.2, as found in
polymerization-grade 1,3-butadiene.
1.4 WARNING—Mercury has been designated by many regulatory agencies as a hazardous materialsubstance that can cause
central nervous system, kidney and liver damage. serious medical issues. Mercury, or its vapor, may has been demonstrated to be
hazardous to health and corrosive to materials. Caution should be taken Use caution when handling mercury and mercury
containing mercury-containing products. See the applicable product Material Safety Data Sheet (MSDS) for details and EPA’s
website—http://www.epa.gov/mercury/faq.htm—for additional information. Users should be aware (SDS) for additional informa-
tion. The potential exists that selling mercury and/or mercury containing products into your state or country may be prohibited by
law.or mercury-containing products, or both, is prohibited by local or national law. Users must determine legality of sales in their
location.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of
the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of
regulatory limitations prior to use.
1.6.1 The user is advised to obtain LPG safety training for the safe operation of this test method procedure and related activities.
1.7 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.
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcommittee
D02.D0.04 on C4 and C5 Hydrocarbons.
Current edition approved April 1, 2015March 1, 2023. Published May 2015June 2023. Originally approved in 1984. Last previous edition approved in 20102015 as
D4423 – 10.D4423 – 10 (2015). DOI: 10.1520/D4423-10R15.10.1520/D4423-23.
*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
D4423 − 23
2. Referenced Documents
2.1 ASTM Standards:
D484 Specification for Hydrocarbon Dry Cleaning Solvents (Withdrawn 1982)
D1193 Specification for Reagent Water
E1 Specification for ASTM Liquid-in-Glass Thermometers
3. Summary of Test Method
3.1 A measured amount of sample is added to an alcoholic hydroxylamine hydrochloride solution that has been adjusted to a given
coloration using either alcoholic acid or base. The carbonyls will react with the hydroxylamine hydrochloride releasing an
equivalent amount of hydrochloric acid which is then back-titrated to the original coloration. A blank containing only methanol
and sample is titrated and the sample’s results are calculated using the blank adjustment. Results are reported as milligrams per
kilogram carbonyls as acetaldehyde.
4. Significance and Use
4.1 The determination of the carbonyl content of polymerization-grade 1,3-butadiene is necessary, since in some polymerization
reactions, the presence of carbonyls in excess over some specified amount can have a deleterious effect upon the polymer properties
or the reaction itself, or both.
5. Apparatus
5.1 Bunsen Valves—A device constructed so that when used with an Erlenmeyer flask, the sample vapors can exit the flask while
protecting the flask’s liquid contents. See Fig. 1 for details.
5.2 Cooling Coil—Prepare a cooling coil by winding about 10 cm to 15 cm of seamless copper tubing (about 6 mm diameter) on
a short length of pipe (about 1.5 cm to 2.0 cm diameter), allowing sufficient length of tubing at the end of the coil to connect it
to the sample source. Attach a valve at a point that would not extend more than 8 cm above the surface of the cooling bath liquid.
To the valve, attach a 6 cm to 8 cm length piece of tubing bent downward so that the hydrocarbon liquid can be directed into the
receiving container.
5.3 Dewar Flask—The Dewar flask must be of sufficient volume to completely immerse the main portion of the cooling coil except
for the extremities necessary for receiving and delivering the sample through the coil.
FIG. 1 Apparatus
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. 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.
D4423 − 23
5.4 Erlenmeyer Flasks, 250 mL capacity.
5.5 Volumetric Flasks, 1 L capacity. These flasks should be Class A glassware.
5.6 Graduated Cylinders—100 mL capacity, glass cylinders, graduated in 1 mL or 2 mL divisions.
5.7 Microburets, 2.00 mL or 5.00 mL capacity. The microburets should be Class A glassware with 0.01 mL or 0.02 mL divisions
or less. It is advisable to have the buret’s tip end equipped with a syringe needle to dispense very small drops of titrant.
5.8 Sample Cylinders—These should be of sufficient volume to give the required amount of sample for testing. Stainless steel
cylinders equipped with needle valves should be used. It is suggested that a 500 mL-capacity cylinder be the minimum size to be
used for butadiene.
5.9 Thermometer—For observing temperatures below −45 °C. The Low Cloud and Pour Point Thermometer, conforming to the
requirements for ASTM Thermometer 6C, as prescribed in Specification E1, is satisfactory. Thermometer 6C has a range from
−80 °C to +20 °C. Temperature measuring devices that cover the temperature range of interest, such as the ASTM 1C thermometer,
or liquid-in-glass thermometers, thermocouples, or platinum resistance thermometers that provide equivalent or better accuracy
and precision may be used.
6. Reagents and Materials
6.1 Purity of Reagents—Reagent grade chemicals should 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 Type II reagent water
conforming to Specification D1193.
6.3 Alcoholic Hydrochloric Acid (0.05N)—Dilute 4.2 mL of concentrated hydrochloric acid (Warning—Poison. Corrosive. May
be fatal if swallowed. Liquid and vapor cause severe burns. Harmful if inhaled.) to volume with anhydrous methanol in a 1 L
volumetric flask. Use the alcoholic 0.05 N potassium hydroxide solution to standardize the HCl solution.
6.4 Alcoholic Hydroxylamine Hydrochloride—Dissolve 35.0 g of hydroxylamine hydrochloride (Warning—May be irritating to
skin, eyes, or mucous membranes. Harmful if inhaled.) in 3.5 L of anhydrous methanol. (Warning—Flammable. Vapor harmful.
May be fatal or cause blindness if swallowed or inhaled. Cannot be made nonpoisonous.)
6.5 Alcoholic Potassium Hydroxide (0.05N)—Dissolve 3.3 g of potassium hydroxide in anhydrous methanol. (Warning—
Corrosive. Can cause severe burns or
...