ASTM D4423-91(1996)

NOTICE: This standard has either been superseded and replaced by a new version or
withdrawn. Contact ASTM International (www.astm.org) for the latest information.
Designation: D 4423 – 91 (Reapproved 1996) An American National Standard
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
Determination of Carbonyls In C Hydrocarbons
This standard is issued under the fixed designation D 4423; 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.
1. Scope 4. Significance and Use
1.1 This test method covers the determination of carbonyls 4.1 The determination of the carbonyl content of
(ketones and aldehydes) in C hydrocarbons. This test method polymerization-grade 1,3-butadiene is necessary, since in some
was tested on polymerization-grade 1,3-butadiene. polymerization reactions, the presence of carbonyls in excess
1.2 The applicable range for this test method is 0 to 50 over some specified amount can have a deleterious effect upon
mg/kg carbonyls calculated as acetaldehyde. the polymer properties or the reaction itself, or both.
1.3 Other C hydrocarbons and their mixtures besides
5. Apparatus
polymerization-grade 1,3-butadiene could be tested using this
5.1 Bunsen Valves—A device constructed so that when used
same test method. However, the precision section of this test
method covers only carbonyls in applicable range as listed in with an Erlenmeyer flask, the sample vapors can exit the flask
while protecting the flask’s liquid contents. See Fig. 1 for
1.2, as found in polymerization-grade 1,3-butadiene.
1.4 The values stated in SI units are to be regarded as the details.
5.2 Cooling Coil—Prepare a cooling coil by winding about
standard.
1.5 This standard does not purport to address all of the 10 to 15 cm of seamless copper tubing (about 6-mm diameter)
on a short length of pipe (about 1.5 to 2.0-cm diameter),
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 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
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. would not extend more than 8 cm above the surface of the
cooling bath liquid. To the valve, attach a 6 to 8 cm length
2. Referenced Documents
piece of tubing bent downward so that the hydrocarbon liquid
2.1 ASTM Standards: can be directed into the receiving container.
D 484 Specification for Hydrocarbon Dry Cleaning Sol- 5.3 Dewar Flask—The Dewar flask must be of sufficient
vents volume to completely immerse the main portion of the cooling
D 1193 Specification for Reagent Water coil except for the extremities necessary for receiving and
E 1 Specification for ASTM Thermometers delivering the sample through the coil.
5.4 Erlenmeyer Flasks. 250-mL capacity.
3. Summary of Test Method
5.5 Volumetric Flasks. 1-L capacity. These flasks should be
3.1 A measured amount of sample is added to an alcoholic Class A glassware.
hydroxylamine hydrochloride solution that has been adjusted
5.6 Graduated Cylinders—100-mL capacity, glass cylin-
to a given coloration using either alcoholic acid or base. The ders, graduated in 1 or 2-mL divisions.
carbonyls will react with the hydroxylamine hydrochloride
5.7 Microburets. 2.00 or 5.00-mL capacity. The microburets
releasing an equivalent amount of hydrochloric acid which is should be Class A glassware with 0.01 or 0.02-mL divisions or
then back-titrated to the original coloration. A blank containing
less. It is advisable to have the buret’s tip end equipped with a
only methanol and sample is titrated and the sample’s results syringe needle to dispense very small drops of titrant.
are calculated using the blank adjustment. Results are reported
5.8 Sample Cylinders—These should be of sufficient vol-
as milligrams per kilogram carbonyls as acetaldehyde. ume 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
This test method is under the jurisdiction of ASTM Committee D-2 on
minumum size to be used for butadiene.
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.D0.04 on C Hydrocarbons. 5.9 Thermometer—For observing temperatures
Current edition approved March 15, 1991. Published July 1991. Originally
below − 45°C. The Low Cloud and Pour Point Thermometer,
published as D 4423 – 84. Last previous edition D 4423 – 84.
conforming to the requirements for ASTM Thermometer 6C,
Discontinued; see 1983 Annual Book of ASTM Standards, Vol. 05.01.
as prescribed in Specification E 1, is satisfactory. Thermometer
Annual Book of ASTM Standards, Vol 11.01
Annual Book of ASTM Standards, Vol 14.03.
D 4423
NOTE 4—Warning: Corrosive. Can cause severe burns or blindness.
Evolution of heat produces a violent reaction or eruption upon too rapid
mixture with water.
6.6 Dry Ice (Carbon Dioxide Solid)—(Warning—See Note
5.)
NOTE 5—Warning: Extremely cold (−78.5°C). Liberates heavy gas
which may cause suffocation. Contact with skin causes burns or freezing,
or both. Vapors may react violently with hot magnesium or aluminum
alloys.
6.7 Stoddard Solvent—Conforming to the specification
listed in Specification D 484. (Warning—See Note 6.)
NOTE 6—Warning: Combustible. Vapor harmful.
6.8 Thymol Blue Indicator—Dissolve 0.04 g of thymol blue
in 100 mL of anhydrous methanol. (Warning—See Note 3.)
7. Preparation of Apparatus
FIG. 1 Apparatus
7.1 Dry Ice-Stoddard Solvent Bath—Add a sufficient quan-
tity of Stoddard solvent into the Dewar flask to ensure that the
6C has a range from − 80 to + 20°C.
cooling coil will be submerged in the liquid plus dry ice (solid
CO ). (Warning—See Note 5 and Note 6.) Carefully add
6. Reagents and Materials
sufficient dry ice to the Stoddard solvent to obtain a tempera-
6.1 Purity of Reagents—Reagent grade chemicals should be
ture of at least − 50°C. (Warning—See Note 7.) Attach the
used in all tests. Unless otherwise indicated, it is intended that
sample cylinder containing the butadiene (Warning—See
all reagents conform to the specifications of the Committee on
Note 8.) to the cooling coil and immerse the coil into the liquid.
Analytical Reagents of the American Chemical Society where
Support the sample cylinder in a cylinder rack or using a ring
such specifications are available. Other grades may be used,
stand and appropriate clamps. Be sure the coil is positioned so
provided it is first ascertained that the reagent is of sufficiently
that the delivery tip is free to dispense liquid butadiene into the
high purity to permit its use without lessening the accuracy of
Erlenmeyer flasks. After each use, be sure to clean the coil’s
the determination.
interior with methanol. DO NOT USE ACETONE.
6.2 Purity of Water—Unless otherwise indicated, references
NOTE 7—Warning: Great care must be taken during this step. Do not
to water shall be understood to mean Type II reagent water
add the dry ice all at once, but in small pieces, especially at the beginning.
conforming to Specification D 1193.
Wear protective gloves and adequate eye protection to prevent any cont
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