ASTM D2384-83(2004)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:D2384–83 (Reapproved 2004)
Standard Test Methods for
Traces of Volatile Chlorides in Butane-Butene Mixtures
This standard is issued under the fixed designation D2384; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope halogen-containingcombustionproductsareabsorbedindilute
sodium carbonate solution.
1.1 These test methods cover the determination of the total
3.1.2 Oxy-Hydrogen Combustion—The sample is burned in
volatile organic chlorides in concentrations from 10 to 100
anoxy-hydrogenatomizerburner,andthecombustionproducts
ppminbutane-butenemixtures.Theamperometricfinishisnot
are absorbed in a dilute solution of sodium carbonate.
directly applicable in the presence of other substances that
3.2 Finishes—Either the amperometric titration or spectro-
combine with silver ion or oxidize chloride ion in dilute acid
photometric finish may be used for the chloride ion determi-
solution. Bromides, sulfides, ammonia, tobacco smoke, and
nation.
more than 25 µg of hydrogen peroxide in the test solution
3.2.1 Amperometric Titration—The chloride ion in aqueous
interfere in the spectrophotometric procedure.
solution is titrated amperometrically with standard silver ni-
1.2 Dissolved sodium chloride is not quantitatively deter-
trate solution, using a saturated calomel electrode as reference
mined using these test methods.
electrode. The diffusion currents are plotted against the corre-
1.3 The values stated in SI units are to be regarded as the
sponding volumes of silver nitrate solution used; the end point
standard.
is taken as the intersection of the two straight-line portions of
1.4 This standard does not purport to address all of the
the curve.
safety concerns, if any, associated with its use. It is the
3.2.2 Spectrophotometric Finish—Chloride ion in the ab-
responsibility of the user of this standard to establish appro-
sorber solution is determined by reaction with mercuric thio-
priate safety and health practices and determine the applica-
cyanate to release thiocyanate, which forms a reddish orange
bility of regulatory limitations prior to use. Specific warning
+++
complex with Fe . The intensity of the color is measured at
statementsaregiveninSections5,8,11,14,19,andAnnexA1.
460 nm with a spectrophotometer or filter photometer.
2. Referenced Documents
4. Significance and Use
2.1 ASTM Standards:
4.1 These test methods are used to determine trace amounts
D329 Specification for Acetone
of volatile chlorides in butane-butene mixtures. Such informa-
D1266 Test Method for Sulfur in Petroleum Products
tionisvaluableincaseswherechlorideisdeleteriousintheuse
(Lamp Method)
of this product; also, chloride contributes to corrosion prob-
3. Summary of Test Methods
lems in processing units in instances where further processing
of this material is involved.
3.1 Combination Test Methods—Either the lamp or oxy-
hydrogen test method may be used for combustion.
5. Purity of Reagents
NOTE 1—Lamp combustion is readily applicable to multiple testing.
5.1 Purity of Reagents—Reagent grade chemicals shall be
Although an oxy-hydrogen burner does not lend itself to multiple testing,
used in all tests. Unless otherwise indicated, it is intended that
itaffordsmuchmorerapidanalysisforasinglesamplethandoesthelamp
all reagents shall conform to the specifications of the Commit-
combustion.
tee onAnalytical Reagents of theAmerican Chemical Society,
3.1.1 Lamp Combustion—Thesampleisburnedinanatmo- 3
where such specifications are available. Other grades may be
sphere of carbon dioxide and oxygen or in purified air; the
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
These test methods are under the jurisdiction of ASTM Committee D02 on
accuracy of the determination.
Petroleum Products and Lubricants and are the direct responsibility of Subcommit-
tee D02.D0 on Hydrocarbons for Chemical and Special Uses.
Current edition approved Nov. 1, 2004. Published November 2004. Originally
´1 3
approved in 1965. Last previous edition approved in 2000 as D2384–83 (2000) . Reagent Chemicals, American Chemical Society Specifications, American
DOI: 10.1520/D2384-83R04. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
For referenced ASTM standards, visit the ASTM website, www.astm.org, or listed by the American Chemical Society, see Analar Standards for Laboratory
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D2384–83 (2004)
5.2 References to water shall be understood to mean 8.3 Sodium Carbonate Absorbent (2 g/L)— Dissolve 2.0 g
chloride-free distilled or deionized water. of anhydrous sodium carbonate (Na CO ) in water and dilute
2 3
5.3 (Warning—In view of the common occurrence of to a litre with water.
chloride in reagents and laboratory air, special care must be
9. Procedure
taken during preparation and storage of reagents to avoid
9.1 Prepare the combustion apparatus as described in Sec-
contamination. They should be isolated from other reagents
tion 7 of Test Method D1266, Preparation ofApparatus, using
and used solely for these methods.Ablank determination must
35 mL of Na CO solution to charge the absorber.
be performed each time a reagent is changed to ensure that it
2 3
9.2 Weigh the vessel containing the sample to the nearest
is not contaminated with chloride.
0.1 g. Support the sample vessel in an upright position so that
It is also imperative that all glassware used in this determi-
the sample is burned from the gaseous phase. Connect the
nation be cleaned thoroughly and rinsed four times with
sample vessel to the auxiliary corrosion-resistant regulating
chloride-free distilled or deionized water. Utmost caution must
valve by means of corrosion-resistant metal tubing (Fig. 1)
be taken during the analysis to prevent contamination from
(Note 2). Connect the bottom valve of the sample vessel to the
chlorides.)
regulated hydrogen supply. By means of short lengths of
6. Sampling
chloride-free rubber tubing, connect the auxiliary valve outlet
to the side inlet of the gas burner and the lower inlet of the gas
6.1 Steam and dry a 10 to 25-mL corrosion-resistant metal
burner (Test Method D1266,AnnexA3,Apparatus Detail, Fig.
sample cylinder having a 450-psi (3100 kPa) working pressure
5) to the burner manifold.
and equipped with a needle valve outlet at each end.
6.2 Pressure the prepared cylinder with dry hydrogen to 20
NOTE 2—For steady burning, it may be necessary to surround the
psig (137.5 kPa gage) to afford a gas cushion preventing
auxiliary valve with a heat-exchanger system. A convenient means is
rupture due to liquid expansion on increase of temperature. winding insulated heating wire, having a resistance of 40 to 60 V, around
theauxiliaryvalveandconnectingittoasuitablerheostat.Anothermeans
6.3 Obtain a liquid sample from the purged sample line,
is to place the regulating valve in a suitable metal beaker and cover the
filling the upright cylinder through the bottom needle valve,
valve body with water maintained at 60 to 80°C.
keepingthetopvalveclosed.Donotpurgethesamplecylinder.
9.3 Open the valve on the sample vessel; then open the
LAMP COMBUSTION TEST METHOD
auxiliary valve to allow a small stream of vapor to escape.
Quickly light the burner. Adjust the flow of CO -O mixture
2 2
7. Apparatus
and the sample so that the flame is approximately 35 mm high
7.1 ASTM Lamp Assembly—Use the apparatus specified in
and clear blue in color; this color is reached just beyond the
Test Method D1266, including the liquefied petroleum gas
point at which a yellow color shows at the tip of the flame.
burner assembly.
Insert the burner into the chimney and readjust the flame if
necessary. When the sample has burned almost to completion,
8. Reagents
openthevalveonthebottomofthesamplevesselandflushthe
8.1 Use the necessary reagents and materials specified in residual sample from the cylinder chamber by passing hydro-
Test Method D1266, in addition to the absorber solution as
gen through the bottom valve for several minutes.
described in 8.3. 9.4 When all of the residual material has been flushed from
8.2 Hydrogen (Warning—Extremely flammable (liquefied)
thesamplevessel,turnoffthehydrogenandclosethevalveson
gas under pressure. See Annex A1.1.) the sample vessel. Disconnect the hydrogen flushing line and
FIG. 1 Diagrammatic Sketch of Butane-Butene Heat Exchange System
D2384–83 (2004)
the line to the heated auxiliary valve and weigh the sample 11. Reagents and Materials
vessel to the nearest 0.1 g. Draw the combustion atmosphere
11.1 Hydrogen (Warning—Extremely flammable (lique-
through one absorber of a set to serve as a blank on the purity
fied) gas under pressure. See Annex A1.1.)
of this atmosphere. Rinse the chimneys and spray traps with
11.2 Oxygen (Warning—Oxygen vigorously accelerates
water and add the rinsings to the absorbers.
combustion. See Annex A1.2.)
9.5 Proceed in accordance with either Section 16 or 21.
11.3 Sodium Carbonate, Absorbent (2g/L)—See 8.3.
OXY-HYDROGEN COMBUSTION TEST METHOD—
12. Procedure
ALTERNATIVE TEST METHOD
12.1 Follow the manufacturer’s instructions for preparing
and operating the apparatus. Place 50 mL of the Na CO
2 3
10. Apparatus
absorbent in the absorber. Burn all of the sample from the gas
10.1 Oxy-Hydrogen Burner —Aflow diagram of a typical
phase of the cylinder (Fig. 1)(Warning—Extremely flam-
apparatus is shown in Fig. 2. The apparatus shall consist of
mable (liquefied) gas under pressure. SeeAnnexA1.1.). Flush
the residual gases from the cylinder chamber by passing
hydrogen through the bottom valve for several minutes, burn-
ing the flushed gases.)
12.2 When combustion is completed, rinse all water-cooled
portions of the apparatus and the spray trap with a spray of
water. Collect all rinsings in the absorbent.
12.3 Proceed in accordance with either Section 16 or 21.
12.4 Prepare a blank by placing 50 mL of the Na CO
2 3
absorbent in the absorber. Operate the apparatus for the same
period of time, under the same conditions that were used for
the combustion of the sample, but without a sample and the
sample inlet closed to the atmosphere. Burn approximately the
same volume of hydrogen as was used to flush the same
cylinder. When combustion of the hydrogen is complete, rinse
all water-cooled portions of the apparatus and the spray trap
with a spray of water. Collect all rinsings in the absorbent.
Proceed as in 12.3.
AMPEROMETRIC TITRATION FINISH
13. Apparatus
13.1 Potentiometer-Galvanometer Assembly, capable of ap-
plyingacellpotentialupto3Vwithanaccuracyof1%offull
1—Atomizer-burner 4—Three-way stopcock
scale, and capable of indicating the cell current by means of a
2—Sample tube 5—Absorber
galvanometer having a sensitivity of 0.005 to 0.008 µA/mm
3—Combustion chamber 6—Spray trap
scale division. A multiposition galvanometer shunt for adjust-
FIG. 2 Flow Diagram of a Typical Oxy-Hydrogen Combustion
ment of current measurement sensitivity should also be pro-
Apparatus
vided; shunt ratios to give sensitivities of approximately 0.05
to 0.08, and 0.10 to 0.16 µA/mm should be included.
13.2 Titration Assembly—An apparatus similar to that
threeparts:atomizer-burner,combustionchamber,andreceiver
shown in Fig. 3, consisting of a rotating (600 rpm) platinum
with spray trap. A blowout safety port in the combustion
chamber is desirable. The remainder of the apparatus shall electrode, a saturated calomel reference electrode with salt
bridge, a means of blanketing the solution with nitrogen, and a
consist of a steel support stand with the necessary needle
valves and flow meters for precise control of air, oxygen, holder for a 10-mL buret.
13.3 Calomel Electrode, constructed as shown in Fig. 3.
hydrogen, and vacuum.
10.2 Vacuum Pump, having a capacity of at least 1200 L/h, 13.4 Platinum Electrode, rotating-hook type. A suitable
electrode may be constructed as follows: Seal a platinum wire
and protected from corrosive fumes by suitable traps.
0.03to0.05in.(0.76to1.3mm)indiameterand0.75to1.0in.
(19.1to25.4mm)longintotheendofa6-mmoutsidediameter
4 soft glass tube that has been shaped into a stirrer blade. Bend
The Wickbold Burner Apparatus obtainable from the Atlas Instrument Co.,
theextendingplatinumwireupwardsatitsmidpointtoforman
8902 E. 11th St., Tulsa, OK, or the Richfield BurnerApparatus obtainable from the
GreinerGlassBlowingLaboratories,3604E.MedfordSt.,LosAngeles,CA90034,
angleof90°.Placeafewdropsofmercuryintheglasstubeand
has been found suitable for this purpose. If you are aware of alternative suppliers,
make electrical contact between the mercury and the connec-
please provide this information to ASTM International Headquarters. Your com-
tion on the amperometric titrator with a piece of copper wire
ments will receive careful consideration at a meeting of the responsible technical
committee , which you may attend. (insulate the exposed wire to prevent shorting).
D2384–83 (2004)
FIG. 3 Schematic Assembly of the Amperometric Titration Cell
13.5 Buret—A 10-mL semi-micro buret, with the tip con- 30%) with 4 volumes of water. Store in a dark-colored
structedsoastobeabletodipbelowthesurfaceofthesolution glass-stoppered bottle.
being titrated.
14.7 Mercury-Calomel Mixture—Prepare a mixture of mer-
cury and calomel (mercurous chloride, Hg Cl ) by vigorously
2 2
14. Reagents
shaking 10 g of calomel with 50 g of mercury, in a glass-
14.1 Acetone (99.5 %) (Warning—Extremely flammable.
stoppered flask, until the calomel becomes uniformly gray in
Vapor may cause fire. See Annex A1.3.)—Refined acetone
color. (Warning—Poison: May be harmful or fatal if inhaled
conforming to Specifications D329.
or swallowed. Vapor harmful, emits toxic fumes when heated.
14.2 Agar Solution—Dissolve2gof agar-agar powder in
Vapor pressure normal room temperature exceeds threshold
100 mL of hot water (80 to 100°C) containing 20 g of
limit value for occupational exposure. See Annex A1.4.)
potassium nitrate (KNO ).
14.8 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
14.3 Bromthymol Blue Indicator
...