ASTM E411-24

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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: E411 − 17a E411 − 24
Standard Test Method for
Trace Quantities of Carbonyl Compounds with 2,4-
Dinitrophenylhydrazine
This standard is issued under the fixed designation E411; 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 carbonyl in the range from 0.50.5 μg to 50 μg calculated as CO.
1.2 This test method is intended to be general and does not include steps for sample preparation.
1.3 Acetals that hydrolyze under the conditions of the test are also determined.
1.4 Carbonyl derivatives such as acetals and imines that are easily hydrolyzed may be determined by an alternative procedure.
1.5 The developed color is not stable and must be measured within a specified period.
NOTE 1—Other test methods for the determination of traces of carbonyl compounds are given in Test Methods D1089, D1612, D2119, and D2191.
1.6 Review the current appropriate Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and
safety precautions.
1.7 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.8 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.
1.9 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. Specific hazards statements are given in Section 7 and Section 8.
1.10 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 D16 on Aromatic, Industrial, Specialty and Related Chemicals and is the direct responsibility of
Subcommittee D16.04 on Instrumental Analysis.
Current edition approved July 1, 2017Jan. 1, 2024. Published July 2017January 2024. Originally approved in 1970. Last previous edition approved in 2017 as
E411 – 17.E411 – 17a. DOI: 10.1520/E0411-17a.10.1520/E0411-24.
*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
E411 − 24
2. Referenced Documents
2.1 ASTM Standards:
D1089 Method of Test for Carbonyl Content of Butadiene (Withdrawn 1984)
D1193 Specification for Reagent Water
D1612 Test Method for Acetone in Methanol (Withdrawn 2011)
D2119 Test Method for Aldehydes in Styrene Monomer
D2191 Test Method for Acetaldehyde Content of Vinyl Acetate
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
E60 Practice for Analysis of Metals, Ores, and Related Materials by Spectrophotometry
E180 Practice for Determining the Precision of ASTM Methods for Analysis and Testing of Industrial and Specialty Chemicals
(Withdrawn 2009)
E300 Practice for Sampling Industrial Chemicals
3. Summary of Test Method
3.1 The sample containing traces of carbonyl compounds is reacted with an acidic solution of 2,4-dinitrophenylhydrazine to form
the hydrazone which, upon reaction with potassium hydroxide, forms a wine-red color, presumably due to a resonating quinoidal
ion. The intensity of the red color, which is a function of the carbonyl concentration, is determined photometrically and the amount
of carbonyl is read directly from a previously prepared calibration curve. This test method is based upon the work of Lappin and
Clark.
4. Significance and Use
4.1 This test method is applicable to the determination of trace amounts of aldehydes and ketones in aqueous solutions and a wide
variety of organic solvents.
5. Interferences
5.1 This test method has been found to be relatively free from interferences. It is necessary, however, to test a sample to ensure
that it does not interfere.
5.2 Carbonyl compounds containing conjugated unsaturation interfere by absorbing at a different wavelength than other carbonyl
compounds.
5.3 Acetals that are only partially hydrolyzed under the conditions of the test will interfere. A higher reaction temperature is
required to effect complete hydrolysis.
5.4 Certain carbonyl compounds such as diisobutyl ketone have been found to undergo incomplete reactions and thus give low
results. These compounds may be determined if a suitable calibration is made using the compound in question.
5.5 Because of the extreme sensitivity of this test method, it is necessary to perform the test in a room from which acetone or other
carbonyl compound vapors are excluded.
6. Apparatus
6.1 Spectrophotometer or Photometer, capable of measuring light absorption at 480 nm and holding a 1-cm1 cm cell.
NOTE 2—If a filter photometer is used, a narrow band filter having its maximum transmission at approximately 480 nm should be used. A discussion of
photometers and photometric practice is given in Practice E60.
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.
Lappin, G. R., and Clark, L. C., Analytical Chemistry, Vol 23, 1951, p. 541.
E411 − 24
6.2 Absorption Cells, 1-cm.1 cm.
6.3 All glassware must be cleaned before use. Rinse thoroughly with water and finally with methanol. Do not use acetone to dry
the glassware.
NOTE 3—The precision and bias reported in this test method were determined using chromic acid cleaning solution to clean the glassware. The effect on
precision and bias of using other cleaning materials has not been determined.
7. Reagents
7.1 Purity of Reagents—Unless otherwise indicated, it is intended that all reagents shall 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.
7.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean Types II or III reagent I or
II reagent water as defined in Specification D1193.
7.3 Methanol, Carbonyl-free—To 4 L of methanol add 20 g of 2,4-dinitrophenylhydrazine and 2 mL of hydrochloric acid (HCl,
sp gr 1.19). Reflux for 2 h and then distill using a 2 to 3-ft2 ft to 3 ft fractionating column. Discard the first 200 mL of distillate.
Continue the distillation until approximately 75 % of the methanol has distilled over.
7.3.1 Warning—Do not allow the pot to begin to go dry because there is danger of a violent decomposition of the
residue.Warning—Do not allow the pot to begin to go dry because there is danger of a violent decomposition of the residue. (See
8.2.) If stored in a tightly capped bottle, the methanol will remain carbonyl-free indefinitely. Properly prepared methanol will have
an absorbance of 0.08 or less when used as a blank (11.2 – 11.4).
7.4 Potassium Hydroxide Solution (100 g/L)—Dissolve 100 g of potassium hydroxide (KOH) in 200 mL of water. Cool and dilute
to 1 L with methanol.
7.5 2,4-Dinitrophenylhydrazine (1 g/L)—Dissolve 0.10 g of 2,4-dinitrophenylhydrazine (Warning—See 8.2Warning—See 8.2) in
50 mL of carbonyl-free methanol containing 4 mL of hydrochloric acid (HCl, sp gr 1.19) and dilute to 100 mL with water. This
solution is unstable and must be discarded after two weeks.
8. Safety Hazards
8.1 Warning—The toxicity of 2,4-dinitrophenylhydrazine has not been established. For this reason, handle with customary care.
Avoid ingestion and contact of the compound with the skin and eyes.Warning—The toxicity of 2,4-dinitrophenylhydrazine has not
been established. For this reason, handle with customary care. Avoid ingestion and contact of the compound with the skin and eyes.
8.2 Warning—2,4-Dinitrophenylhydrazine is an explosive and may ignite violently in contact with an open flame or electrical
spark. Handle with caution. Avoid all sources of heat.Warning—2,4-Dinitrophenylhydrazine is an explosive and may ignite
violently in contact with an open flame or electrical spark. Handle with caution. Avoid all sources of heat.
9. Sampling
9.1 Special precautions may be necessary to ensure that the sample taken for analysis is representative of the whole. Refer to
Practice E300 for a detailed discussion of sampling procedures.
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.
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