ASTM D2192-96

NOTICE: This standard has either been superseded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
Designation: D 2192 – 96
AMERICAN SOCIETY FOR TESTING AND MATERIALS
100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM
Standard Test Method for
Purity of Aldehydes and Ketones
This standard is issued under the fixed designation D 2192; 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 (e) indicates an editorial change since the last revision or reapproval.
NH OH·HCl 1 HOCH CH N→ (1)
1. Scope ~ !
2 2 2 3
NH OH 1 ~HOCH CH ! N·HCl
1.1 This test method covers the determination of the purity
2 2 2 3
of certain commercially available aldehydes and ketones.
The free hydroxylamine reacts with the aldehyde or ketone
1.2 In addition to all aldehydes and ketones, all compounds
to form the corresponding oxime.
such as vinyl alkyl ethers, acetals, and ketals, that hydrolyze
RR C50 1 NH OH → RR C5H5NOH 1 H O, (2)
1 2 1 2
under the conditions of the reaction to form free carbonyl
groups, react with the reagent and consequently interfere.
where:
Water, alcohols, saturated esters, and hydrocarbons do not react
R 5 alkyl group and
with the reagent, but large amounts of inert organic solvents are R 5 alkyl group or hydrogen.
undesirable because of the effect on the indicator.
The amount of hydroxylamine consumed, which is deter-
1.3 This standard does not purport to address all of the mined by titration of the excess base with standard sulfuric
safety concerns, if any, associated with its use. It is the
acid, is a measure of the aldehyde or ketone originally present.
responsibility of the user of this standard to establish appro- 3.2 Since the determination is based on an acidimetric
priate safety and health practices and determine the applica-
titration, a suitable correction must be applied if the sample is
bility of regulatory limitations prior to use. For specific hazard not neutral to bromophenol blue indicator.
statements, see Note 1 and Note 2.
4. Significance and Use
1.4 For hazard information and guidance, see the supplier’s
Material Safety Data Sheet. 4.1 This test method provides a measurement of purity
(assay) of aldehydes and ketones. The results of these mea-
2. Referenced Documents
surements can be used for specification acceptance.
2.1 ASTM Standards:
4.2 The precision of this test method is applicable only to
D 268 Guide for Sampling and Testing Volatile Solvents material having a purity of 98 to 100 %.
and Chemical Intermediates for Use in Paint and Related
5. Apparatus
Coatings and Materials
D 1193 Specification for Reagent Water 5.1 Pressure Bottle, 200 to 350-mL capacity, with lever type
closure and made of heat-resistant glass.
E 200 Practice for Preparation, Standardization, and Stor-
age of Standard and Reagent Solutions for Chemical 5.2 Container for Pressure Bottle—A suitable safety device
Analysis to contain the pressure bottle. A metal container with a hinged
E 222 Test Methods for Hydroxyl Groups by Acetic Anhy- top and perforated bottom, a strong synthetic fabric or canvas
dride Acetylation bag, or a safety shield may be used.
5.3 Ampoule, 1 or 2-mL capacity.
3. Summary of Test Method
5.4 Weighing Pipet, Lunge or similar type.
3.1 Hydroxylamine hydrochloride is converted in part to
5.5 Burets, 50-mL capacity.
free hydroxylamine by reaction with a known amount of 5.6 Transfer Pipet, 50-mL capacity.
aqueous triethanolamine.
5.7 Glass Rod, 8-mm, several pieces approximately 1 in.
long.
5.8 Boiling Water Bath.
This test method is under the jurisdiction of ASTM Committee D-1 on Paint
and Related Coatings, Materials, and Applications and is the direct responsibility of
6. Reagents and Materials
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates.
6.1 Purity of Reagents—Reagent grade chemicals shall be
Current edition approved May 10, 1996. Published July 1996. Originally
published as D 2192 – 63. Last previous edition D 2192 – 89.
used in all tests. Unless otherwise indicated, it is intended that
Annual Book of ASTM Standards, Vol 06.04.
all reagents shall conform to the specifications of the Commit-
Annual Book of ASTM Standards, Vol 11.01.
4 tee on Analytical Reagents of the American Chemical Society,
Annual Book of ASTM Standards, Vol 15.05.
D 2192
where such specifications are available. Other grades may be substantially pure material, weigh the specimen to the nearest
used, provided it is first ascertained that the reagent is of 0.1 mg, using the amount and procedure specified in Table 1.
sufficiently high purity to permit its use without lessening the
NOTE 1—Precaution: Acetaldehyde is a highly volatile, flammable
accuracy of the determination.
material; observe all necessary safety precautions. Handle samples only in
6.2 Purity of Water—Unless otherwise indicated, references
a fume hood that is free from open flames, electric heaters, and other
to water shall be understood to mean reagent water conforming sources of ignition. Cool all samples in an ice bath before the containers
are opened. Weigh the acetaldehyde in a sealed glass ampoule. The actual
to Type IV of Specification D 1193.
procedure for filling and sealing the ampoule will vary somewhat with the
6.3 Bromophenol Blue Indicator (0.04 % Alcoholic
type of ampoule being used. One convenient method is to pack commer-
Solution)—Dissolve 0.04 g of bromophenol blue (tetrabro-
cially available ampoules in powdered, solid carbon dioxide, introduce the
mophenolsulfonphthalein) in 100 mL of methyl alcohol. Titrate
specimen by means of a chilled hypodermic syringe, and seal the ampoule
this solution with 0.1 N sodium hydroxide (NaOH) solution to
with a gas torch.
a reddish-bronze color. If an off-color is obtained at this point,
7.7 If a sealed glass ampoule is used to weigh the specimen,
it is probably due to the age of the indicator and fresh indicator
add several pieces of 8-mm glass rod and shake the bottle
should be used to prepare a new solution.
vigorously to break the ampoule.
6.4 Cylinder Nitrogen.
7.8 React the solutions at room temperature or at 98°C
6.5 Hydroxylamine Hydrochloride, Standard (0.5 N Alco-
according to the directions in Table 1.
holic Solution)—Dissolve 35 g of hydroxylamine hydrochlo-
7.8.1 Reaction at 98°C (Precaution—See Note 2.)—Place
ride (NH OH · HCl) in 150 mL of water and dilute to 1 L with
the specimen and blank bottles as close together as possible in
99 % isopropanol.
a boiling water bath maintained at least at 98°C for the time
6.6 Isopropanol (99 %).
specified in Table 1. Maintain sufficient water in the bath to just
6.7 Sulfuric Acid, Standard (0.5 N)—Prepare and standard-
cover the liquid in the bottles. Remove the bottles from the
ize 0.5 N sulfuric acid (H SO ) in accordance with Practice
2 4
bath after the specified time and allow them to cool in air to
E 200, Sections 24 through 27.
room temperature. When the bottles have cooled, remove them
6.8 Triethanolamine, Standard (0.5 N Aqueous Solution)—
from the safety device and continue as described in 7.9.
Dissolve 65 mL (74 g) of 98 % triethanolamine in water and
dilute to 1 L with water. Adjust the normality of this solution NOTE 2—Precaution: Enclose each bottle securely in a suitable con-
tainer (metal or strong fab
...