ASTM D2384-83(2009)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D2384 − 83(Reapproved 2009)
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.
NOTE 1—Lamp combustion is readily applicable to multiple testing.
1. Scope
Although an oxy-hydrogen burner does not lend itself to multiple testing,
1.1 These test methods cover the determination of the total
itaffordsmuchmorerapidanalysisforasinglesamplethandoesthelamp
volatile organic chlorides in concentrations from 10 to 100 combustion.
ppminbutane-butenemixtures.Theamperometricfinishisnot
3.1.1 Lamp Combustion—The sample is burned in an atmo-
directly applicable in the presence of other substances that
sphere of carbon dioxide and oxygen or in purified air; the
combine with silver ion or oxidize chloride ion in dilute acid
halogen-containingcombustionproductsareabsorbedindilute
solution. Bromides, sulfides, ammonia, tobacco smoke, and
sodium carbonate solution.
more than 25 µg of hydrogen peroxide in the test solution
3.1.2 Oxy-Hydrogen Combustion—The sample is burned in
interfere in the spectrophotometric procedure.
anoxy-hydrogenatomizerburner,andthecombustionproducts
1.2 Dissolved sodium chloride is not quantitatively deter-
are absorbed in a dilute solution of sodium carbonate.
mined using these test methods.
3.2 Finishes—Either the amperometric titration or spectro-
1.3 The values stated in SI units are to be regarded as
photometric finish may be used for the chloride ion determi-
standard. No other units of measurement are included in this
nation.
standard.
3.2.1 Amperometric Titration—The chloride ion in aqueous
solution is titrated amperometrically with standard silver ni-
1.4 This standard does not purport to address all of the
trate solution, using a saturated calomel electrode as reference
safety concerns, if any, associated with its use. It is the
electrode. The diffusion currents are plotted against the corre-
responsibility of the user of this standard to establish appro-
sponding volumes of silver nitrate solution used; the end point
priate safety and health practices and determine the applica-
is taken as the intersection of the two straight-line portions of
bility of regulatory limitations prior to use. Specific warning
the curve.
statements are given in Sections 5, 8, 11, 14, 19, and Annex
A1.
3.2.2 Spectrophotometric Finish—Chloride ion in the ab-
sorber solution is determined by reaction with mercuric thio-
2. Referenced Documents
cyanate to release thiocyanate, which forms a reddish orange
+++
2.1 ASTM Standards:
complex with Fe . The intensity of the color is measured at
D329Specification for Acetone
460 nm with a spectrophotometer or filter photometer.
D1266TestMethodforSulfurinPetroleumProducts(Lamp
Method)
4. Significance and Use
3. Summary of Test Methods 4.1 These test methods are used to determine trace amounts
of volatile chlorides in butane-butene mixtures. Such informa-
3.1 Combination Test Methods—Either the lamp or oxy-
tionisvaluableincaseswherechlorideisdeleteriousintheuse
hydrogen test method may be used for combustion.
of this product; also, chloride contributes to corrosion prob-
lems in processing units in instances where further processing
These test methods are under the jurisdiction of ASTM Committee D02 on
of this material is involved.
PetroleumProductsandLubricantsandarethedirectresponsibilityofSubcommittee
D02.D0.04 on C4 Hydrocarbons.
Current edition approved July 1, 2009. Published November 2009. Originally
5. Purity of Reagents
approved in 1965. Last previous edition approved in 2004 as D2384–83(2004).
DOI: 10.1520/D2384-83R09.
5.1 Purity of Reagents—Reagent grade chemicals shall be
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
used in all tests. Unless otherwise indicated, it is intended that
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
all reagents shall conform to the specifications of the Commit-
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. tee onAnalytical Reagents of theAmerican Chemical Society,
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D2384 − 83 (2009)
FIG. 1 Diagrammatic Sketch of Butane-Butene Heat Exchange System
where such specifications are available. Other grades may be LAMP COMBUSTION TEST METHOD
used, provided it is first ascertained that the reagent is of
7. Apparatus
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
7.1 ASTM Lamp Assembly—Use the apparatus specified in
Test Method D1266, including the liquefied petroleum gas
5.2 References to water shall be understood to mean
burner assembly.
chloride-free distilled or deionized water.
5.3 (Warning—In view of the common occurrence of
8. Reagents
chloride in reagents and laboratory air, special care must be
8.1 Use the necessary reagents and materials specified in
taken during preparation and storage of reagents to avoid
Test Method D1266, in addition to the absorber solution as
contamination. They should be isolated from other reagents
described in 8.3.
andusedsolelyforthesemethods.Ablankdeterminationmust
be performed each time a reagent is changed to ensure that it
8.2 Hydrogen (Warning—Extremely flammable (liquefied)
is not contaminated with chloride.
gas under pressure. See Annex A1.1.)
It is also imperative that all glassware used in this determi-
8.3 Sodium Carbonate Absorbent (2 g/L)— Dissolve 2.0 g
nation be cleaned thoroughly and rinsed four times with
of anhydrous sodium carbonate (Na CO ) in water and dilute
2 3
chloride-freedistilledordeionizedwater.Utmostcautionmust
to a litre with water.
be taken during the analysis to prevent contamination from
chlorides.)
9. Procedure
9.1 Prepare the combustion apparatus as described in Sec-
6. Sampling
tion 7 of Test Method D1266, Preparation ofApparatus, using
6.1 Steam and dry a 10 to 25-mL corrosion-resistant metal
35 mL of Na CO solution to charge the absorber.
2 3
samplecylinderhavinga450-psi(3100kPa)workingpressure
9.2 Weigh the vessel containing the sample to the nearest
and equipped with a needle valve outlet at each end.
0.1 g. Support the sample vessel in an upright position so that
6.2 Pressure the prepared cylinder with dry hydrogen to 20
the sample is burned from the gaseous phase. Connect the
psig (137.5 kPa gage) to afford a gas cushion preventing
sample vessel to the auxiliary corrosion-resistant regulating
rupture due to liquid expansion on increase of temperature.
valve by means of corrosion-resistant metal tubing (Fig. 1)
6.3 Obtain a liquid sample from the purged sample line,
(Note 2). Connect the bottom valve of the sample vessel to the
filling the upright cylinder through the bottom needle valve,
regulated hydrogen supply. By means of short lengths of
keepingthetopvalveclosed.Donotpurgethesamplecylinder.
chloride-free rubber tubing, connect the auxiliary valve outlet
to the side inlet of the gas burner and the lower inlet of the gas
burner (Test Method D1266,AnnexA3,Apparatus Detail, Fig.
Reagent Chemicals, American Chemical Society Specifications, American 5) to the burner manifold.
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
NOTE 2—For steady burning, it may be necessary to surround the
listed by the American Chemical Society, see Annual Standards for Laboratory
auxiliary valve with a heat-exchanger system. A convenient means is
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, winding insulated heating wire, having a resistance of 40 to 60Ω, around
MD. theauxiliaryvalveandconnectingittoasuitablerheostat.Anothermeans
D2384 − 83 (2009)
is to place the regulating valve in a suitable metal beaker and cover the
valve body with water maintained at 60 to 80°C.
9.3 Open the valve on the sample vessel; then open the
auxiliary valve to allow a small stream of vapor to escape.
Quickly light the burner. Adjust the flow of CO -O mixture
2 2
and the sample so that the flame is approximately 35 mm high
and clear blue in color; this color is reached just beyond the
point at which a yellow color shows at the tip of the flame.
Insert the burner into the chimney and readjust the flame if
necessary. When the sample has burned almost to completion,
openthevalveonthebottomofthesamplevesselandflushthe
residual sample from the cylinder chamber by passing hydro-
gen through the bottom valve for several minutes.
9.4 When all of the residual material has been flushed from
thesamplevessel,turnoffthehydrogenandclosethevalveson
the sample vessel. Disconnect the hydrogen flushing line and
the line to the heated auxiliary valve and weigh the sample
vessel to the nearest 0.1 g. Draw the combustion atmosphere
through one absorber of a set to serve as a blank on the purity
of this atmosphere. Rinse the chimneys and spray traps with
water and add the rinsings to the absorbers.
9.5 Proceed in accordance with either Section 16 or 21.
1—Atomizer-burner 4—Three-way stopcock
2—Sample tube 5—Absorber
3—Combustion chamber 6—Spray trap
OXY-HYDROGEN COMBUSTION TEST METHOD—
ALTERNATIVE TEST METHOD
FIG. 2 Flow Diagram of a Typical Oxy-Hydrogen Combustion
Apparatus
10. Apparatus
10.1 Oxy-Hydrogen Burner —Aflow diagram of a typical
mable (liquefied) gas under pressure. SeeAnnex A1.1.). Flush
apparatus is shown in Fig. 2. The apparatus shall consist of
the residual gases from the cylinder chamber by passing
threeparts:atomizer-burner,combustionchamber,andreceiver
hydrogen through the bottom valve for several minutes, burn-
with spray trap. A blowout safety port in the combustion
ing the flushed gases.)
chamber is desirable. The remainder of the apparatus shall
12.2 When combustion is completed, rinse all water-cooled
consist of a steel support stand with the necessary needle
portions of the apparatus and the spray trap with a spray of
valves and flow meters for precise control of air, oxygen,
water. Collect all rinsings in the absorbent.
hydrogen, and vacuum.
12.3 Proceed in accordance with either Section 16 or 21.
10.2 Vacuum Pump, having a capacity of at least 1200 L/h,
and protected from corrosive fumes by suitable traps.
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
11. Reagents and Materials
period of time, under the same conditions that were used for
11.1 Hydrogen (Warning—Extremely flammable (lique-
the combustion of the sample, but without a sample and the
fied) gas under pressure. See Annex A1.1.)
sample inlet closed to the atmosphere. Burn approximately the
same volume of hydrogen as was used to flush the same
11.2 Oxygen (Warning—Oxygen vigorously accelerates
cylinder. When combustion of the hydrogen is complete, rinse
combustion. See Annex A1.2.)
all water-cooled portions of the apparatus and the spray trap
11.3 Sodium Carbonate, Absorbent (2g/L)—See 8.3.
with a spray of water. Collect all rinsings in the absorbent.
Proceed as in 12.3.
12. Procedure
12.1 Follow the manufacturer’s instructions for preparing
AMPEROMETRIC TITRATION FINISH
and operating the apparatus. Place 50 mL of the Na CO
2 3
13. Apparatus
absorbent in the absorber. Burn all of the sample from the gas
phase of the cylinder (Fig. 1)(Warning —Extremely flam-
13.1 Potentiometer-Galvanometer Assembly, capable of ap-
plyingacellpotentialupto3Vwithanaccuracyof1%offull
4 scale, and capable of indicating the cell current by means of a
The Wickbold Burner Apparatus obtainable from the Atlas Instrument Co.,
galvanometer having a sensitivity of 0.005 to 0.008 µA/mm
8902 E. 11th St., Tulsa, OK, or the Richfield BurnerApparatus obtainable from the
GreinerGlassBlowingLaboratories,3604E.MedfordSt.,LosAngeles,CA90034,
scale division. A multiposition galvanometer shunt for adjust-
has been found suitable for this purpose. If you are aware of alternative suppliers,
ment of current measurement sensitivity should also be pro-
please provide this information to ASTM International Headquarters. Your com-
vided; shunt ratios to give sensitivities of approximately 0.05
ments will receive careful consideration at a meeting of the responsible technical
committee, which you may attend. to 0.08, and 0.10 to 0.16 µA/mm should be included.
D2384 − 83 (2009)
FIG. 3 Schematic Assembly of the Amperometric Titration Cell
13.2 Titration Assembly—An apparatus similar to that 14.2 Agar Solution—Dissolve2gof agar-agar powder in
shown in Fig. 3, consisting of a rotating (600 rpm) platinum 100 mL of hot water (80 to 100°C) containing 20 g of
electrode, a saturated calomel reference electrode with salt potassium nitrate (KNO ).
bridge, a means of blanketing the solution with nitrogen, and a
14.3 Bromthymol Blue Indicator Solution—Dissolve0.10g
holder for a 10-mL buret.
of the solid indicator in 100 mL of hot water, cool, and add 1
13.3 Calomel Electrode, constructed as shown in Fig. 3.
mLof chloroform as a preservative. Discard the solution when
it is 1 week old.
13.4 Platinum Electrode, rotating-hook type. A suitable
electrode may be constructed as follows: Seal a platinum wire
NOTE 3—Remove possible objectionable amounts of chloride by
0.03to0.05in.(0.76to1.3mm)indiameterand0.75to1.0in.
passing the solution through an ion-exchange resin in the hydroxyl form.
(19.1to25.4mm)longintotheendofa6-mmoutsidediameter Neutralizetheresultingalkalinesolutiontothebromthymolblueendpoint
by titration with HNO (3+97).
soft glass tube that has been shaped into a stirrer blade. Bend
−
theextendingplatinumwireupwardsatitsmidpointtoforman
14.4 Chloride, Standard Solution (10 µg Cl /mL)—Dilute a
angleof90°.Placeafewdropsofmercuryintheglasstubeand
suitable volume of 1+10 assayed hydrochloric acid to obtain
−
make electrical contact between the mercury and the connec-
a solution containing 10 µg Cl /mL.
tion on the amperometric titrator with a piece of copper wire
14.5 Gelatin Solution (10 g/L)—Dissolve1gof gelatin in
(insulate the exposed wire to prevent shorting).
100 mL of hot water and add 1 mL of chloroform as a
13.5 Buret—A 10-mL semi-micro buret, with the tip con-
preservative. Discard the solution when it is 1 week old.
structedsoastobeabletodipbelowthesurfaceofthesolution
14.6 Hydrogen Peroxide Solution—Prepare b
...