ASTM D5507-99(2008)e1
(Test Method)Standard Test Method for Determination of Trace Organic Impurities in Monomer Grade Vinyl Chloride by Capillary Column/Multidimensional Gas Chromatography
Standard Test Method for Determination of Trace Organic Impurities in Monomer Grade Vinyl Chloride by Capillary Column/Multidimensional Gas Chromatography
SIGNIFICANCE AND USE
The multidimensional approach permits all of the trace impurities to be well separated from the main vinyl chloride peak, thereby improving quantitative accuracy over established packed column methods.
The minimum detection limit (MDL) for all components of interest has been shown to be well below 500 ppb for this test method.
SCOPE
1.1 This is a general-purpose capillary-based test method for the determination of trace level impurities in high-purity vinyl chloride. This test method uses serially coupled capillary PLOT columns in conjunction with the multidimensional techniques of column switching and cryogenic trapping to permit the complete separation of the 11 key vinyl chloride impurities in a single 25-min run.
Note 1—There is no known ISO equivalent to this standard.
1.2 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 and health practices and determine the applicability of regulatory limitations prior to use. Specific hazards statements are given in Section 8.
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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
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Designation: D5507 − 99(Reapproved 2008)
Standard Test Method for
Determination of Trace Organic Impurities in Monomer
Grade Vinyl Chloride by Capillary Column/Multidimensional
Gas Chromatography
This standard is issued under the fixed designation D5507; 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.
´ NOTE—Editorially updated ISO statement in Note 1, and reviewed standard for mercury references in March 2008.
1. Scope* valveoralternatelyasanexpandedgas.Anappropriatevolume
of the liquid or gas sample is injected to enable the required
1.1 This is a general-purpose capillary-based test method
detection limits to be achieved.Apreliminary GC separation is
for the determination of trace level impurities in high-purity
achieved on a 6-m pre-column, the purpose of which is to
vinyl chloride. This test method uses serially coupled capillary
removethebulkofthevinylchloridepeakfromthetracepeaks
PLOT columns in conjunction with the multidimensional
of interest. Two heart-cut transfers are made from this pre-
techniques of column switching and cryogenic trapping to
column separation, which sends selected portions to a second
permit the complete separation of the 11 key vinyl chloride
column for additional separation. These two cuts incorporate
impurities in a single 25-min run.
10 of the 11 trace impurities of interest, but they exclude 1,2
NOTE 1—There is no known ISO equivalent to this standard.
ethylenedichlorideandthebulkofthevinylchloridepeak.The
1.2 This standard does not purport to address all of the
1,2 EDC peak is eluted from the 6-m pre-column and detected
safety concerns, if any, associated with its use. It is the at the first FID after the two cuts are made.
responsibility of the user of this standard to establish appro-
4.2 The components eluting to the two FID detectors are
priate safety and health practices and determine the applica-
identified and quantitated by comparing their retention times
bility of regulatory limitations prior to use. Specific hazards
and area counts to those obtained previously from a calibration
statements are given in Section 8.
standard run under identical conditions.
2. Referenced Documents
5. Significance and Use
2.1 ASTM Standards:
5.1 The multidimensional approach permits all of the trace
D883 Terminology Relating to Plastics
impurities to be well separated from the main vinyl chloride
D1600 TerminologyforAbbreviatedTermsRelatingtoPlas-
peak,therebyimprovingquantitativeaccuracyoverestablished
tics
packed column methods.
F307 Practice for Sampling Pressurized Gas for Gas Analy-
sis 5.2 Theminimumdetectionlimit(MDL)forallcomponents
of interest has been shown to be well below 500 ppb for this
3. Terminology
test method.
3.1 Definitions—Terminology is in accordance with Termi-
nologies D883 and D1600 unless otherwise indicated. 6. Apparatus
6.1 Instrumentation:
4. Summary of Test Method
3,4
6.1.1 HP 5890A (or equivalent), equipped as follows:
4.1 The liquid vinyl chloride sample or calibration standard
6.1.1.1 Split/Splitless Injector System—Must be demon-
is injected either directly using a high-pressure liquid sampling
strated to be free of discrimination effects induced by vapor
viscositydifferencesifhelium-ornitrogen-basedgasstandards
This test method is under the jurisdiction ofASTM Committee D20 on Plastics
are to be used for instrument calibration.
and is the direct responsibility of Subcommittee D20.70 on Analytical Methods.
Current edition approved March 1, 2008. Published March 2008. Originally
approved in 1994. Last previous edition approved in 1999 as D5507 - 99. DOI:
10.1520/D5507-99R08E01. The sole source of supply of the apparatus known to the committee at this time
For referenced ASTM standards, visit the ASTM website, www.astm.org, or is Hewlett-Packard Co., 3495 Deer Creek Road, Palo Alto, California 94304.
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM If you are aware of alternative suppliers, please provide this information to
Standards volume information, refer to the standard’s Document Summary page on ASTM International Headquarters. Your comments will receive careful consider-
the ASTM website. ation at a meeting of the responsible technical committee, which you may attend.
*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
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D5507 − 99 (2008)
7. Reagents and Materials
7.1 Helium—Carrier gas, zero grade, high quality. Traps
should be placed in the supply lines leading to the gas
chromatograph. These traps should reduce oxygen, moisture,
and hydrocarbons to the lowest possible levels.
7.2 Hydrogen—Flame gas, high-purity (hydrocarbon free).
7.3 Air—Flame gas, high-purity (hydrocarbon free).
7.4 Liquid CO —Coolant, bone-dry grade, liquid-delivery,
1200-psi helium pad recommended.
7.5 Standards:
7.5.1 Primary Standard—Theprimarystandardisacertified
reference standard, which is blended into a stable nitrogen or
helium matrix. The component concentrations should be pre-
pared and reported on an as-in-vinyl chloride basis. The
concentrations of the various components in this standard
should also represent typical values expected for the particular
process or sample. The following is a typical calibration
standard composition:
FIG. 1 Procedure B: On-Line Vaporization Using the LPG Vapor-
Component Mole, ppm Weight, ppm
izing Injector
Ethylene 29.4 13.2
Propylene 20.0 13.5
6.1.1.2 Dual Flame-Ionization Detectors.
Acetylene 6.8 2.8
6.1.1.3 Column Switching Device A pneumatics control Butane-1 6.8 6.1
4,5 Trans-butene-2 7.1 6.4
system, available from Scientific Glass Engineering, Inc., or
Cis-butene-2 7.5 6.7
equivalent.
1,3 butadiene 6.5 5.6
Methyl chloride 36.8 29.7
6.1.1.4 Sub-Ambient Oven Temperature Control (optional).
Vinyl acetylene 12.2 10.2
6.1.1.5 LPG Vaporizing Injector, available from Microana-
Ethyl chloride 15.9 16.4
4,6
lytics Instrumentation, or equivalent (Fig. 1).
1,2 ethylene dichloride 11.8 18.7
Nitrogen balance
3,4
6.2 Data System—Dual HP3396AIntegrators (or equiva-
7.5.2 Secondary Standard—The secondary standard is a
lent) permit the acquisition, storage, and reduction of the
vinylchloride-basedblend,whichisusedformethodsetupand
output signals from the two FIDs simultaneously. After the
day-to-day method calibration. This standard is prepared from
initial method development, however, it is possible to consoli-
actual vinyl chloride product, which is spiked where appropri-
date the output to a single integrator using the instruments
ate to yield the approximate levels represented in the nitrogen-
signal switching capability.
based primary standard. The final concentrations should be
6.3 Columns:
determined by averaging the results from multiple runs, which
6.3.1 Pre-Column—100 cm of 0.20-mm inside diameter
are referenced to the primary standard. This calibration/
fused silica fixed restrictor coupled to the front ofa6mby
recalibration process may be conducted using an alternate GC
TM
0.53-mm inside diameter GSQ available from J & W
procedure.
4,7
Scientific (or equivalent).
6.3.2 Analytical Column—9 m by 0.53-mm inside diameter
8. Hazards
TM 4,7
GSQ available from J & W Scientific (or equivalent) plus
TM
8.1 Appropriate caution must be exercised in handling the
25 m by 0.53 mm inside diameter PORAPLOT U
4,8
sample due to the suspected carcinogenicity of vinyl chloride.
Chrompack (or equivalent).
Any excess of sample beyond that actually injected into the
6.4 Syringes—A range of high-quality gas-tight syringes
column should be routed to a purge waste line to be passed to
representing volumes from 0.5 to 25 mL should be available.
a vent hood or other suitable disposal location. This excess
These syringes should be equipped with PTFE-tipped plunger
sampleincludestheinletsplitterventflowandthesample-loop
seals and on and off syringe valves to prevent the loss of gas
purge flow in the case in which a gas-valve injection is being
sample.
made.
5 9. Sampling
The sole source of supply of the apparatus known to the committee at this time
is Scientific Glass Engineering 2007 Kramer Lane, Austin, Texas 78758.
9.1 This section is to be followed for all samples, including
The sole source of supply of the apparatus known to the committee at this time
unknown samples and the synthetic standards.
is Microanalytics Instrumentation, 2713 Sam Bass Rd., Round Rock, TX 78681.
The sole source of supply of the apparatus known to the committee at this time
9.2 Samples should be supplied to the laboratory in high-
is J & W Scientific, 91 Blue Ravine Road, Folsom, California 95630-4714.
pressure sample cylinders, obtained using the procedure de-
The sole source of supply of the apparatus known to the committee at this time
is Chrompack Inc., 1130 Route 202, Raritan, NJ 08869. scribed in Practice F307 or similar standards.
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D5507 − 99 (2008)
E. Open Valve A and then Valve B. The liquid will expand,
filling the larger cylinder. Close Valve A and disconnect at E.
NOTE 2—To prevent possible rupture of the liquid-filled pipe cylinder,
the sample cylinder and its contents should be at room temperature prior
to sampling, and the liquid should be allowed to remain in the pipe
cylinder for only a minimum of time.
(2) Connect the cylinder containing the vaporized sample to
thechromatographgasvalve.Evacuatethesampleloopandthe
lines up to the sample cylinder. Close the valve to the vacuum
source and allow the sample loop to fill with sample up to
atmospheric pressure. Repeat the evacuation and filling of the
sample loop with vaporized sample. Turn the valve so that the
vaporized sample is displaced with carrier gas into the chro-
matograph.
9.5.2.2 Procedure B—On-line vaporization using the LPG
Vaporizing Injector (or equivalent).An alternate approach that
has been used successfully for the automated on-line LPG to
vapor conversion and sample introduction is shown in Fig. 1.
The vapor injection occurs in the upper half of this assembly
FIG. 2 Procedure A: Off-Line Vaporization
labeled “hot zone.” The automated injection process proceeds
as follows:
(1) The lower valve of the sample cylinder is opened to
9.3 Placethecylinderinahorizontalpositioninasafeplace
permit the flow of liquid to the fixed restricter (35 to 45-µm
such as a hood. Check to see that the container is at least
pinpoint restriction or equivalent).
one-half full by opening the valve slightly. The container is at
least one-half full if liquid is emitted (a white cloud of vapors). (2) The constant-pressure force above the liquid drives
liquid across the fixed restrictor at a constant rate.
Donotanalyzeanysamplesoruseanysyntheticstandardifthe
liquid in the container is below this amount. (3) The vapor formed in the heated vaporizer tube is mixed
prior to passing through the block out valve and on through the
9.4 Placethecylinderinaverticalpositionandrepressureto
sample loop to vent.
1.208 MPa (175 psig) with the chromatographic carrier or
(4) The sample loop purge is permitted to proceed for a
equivalentinertgasthroughthevalveatthetopofthecylinder,
fixedperiodoftimethatissufficienttoensureacompletepurge
ensuring that no air enters during the operation.
of the loop volume.
9.5 Useeitherofthefollowingtwoproceduresforobtaining
(5) The block out valve automatically shuts off the flow of
a sample from the container:
vapor to the sample loop after the sample-loop purge period.
9.5.1 Liquid Sample—Connect the cylinder to the liquid
(6) Ashort delay period is permitted after sample block out
valve on the chromatograph using a minimum length of
andbeforesampleinjection.Thisdelayensuresthatthesample
connecting tubing, so that sample is withdrawn from the
loop is permitted to decay back to atmospheric pressure.
bottom of the cylinder and a liquid sample is obtained. The
(7) The gas sampling valve is then actuated to inject the
liquid valve on the chromatograph must be designed in such a
sample loop contents into the flowing carrier gas stream and
mannerthatfullsamplepressurecanbemaintainedthroughthe
simultaneously begin the GC run.
valve without leaking and that means are provided for trapping
a liquid sample in the chromatograph valve under static flow
10. Preparation of Apparatus
conditions. With the exit of the chromatograph valve closed,
10.1 The column/transfer tube combination is installed as
open the valve on the cylinder. Open the exit from the
outlined in the schematic shown in Fig. 3 (by-pass operation)
chromatograph valve slowly so that liquid flows through the
and Fig. 4 (heart-cut operation).
connecting line and valve. Close the exits so that the liquid
sample is trapped in the valve. Perform the necessary opera- 10.2 Initial Instrument Parameters:
tions to introduce the liquid sample into the chromatograph 10.2.1 Columns:
column. 10.2.1.1 Pre-Column—100 cm of 0.20-mm inside diameter
9.5.2 Vaporized Sample: fused silica fixed restrictor coupled to the front ofa6mby
TM
9.5.2.1 Procedure A—Off-Line Vaporization: 0.53-mm inside diameter GCQ available from J & W
4,7
(1) Assemble the apparatus in a manner similar to that Scientific (or equivalent).
illustratedinFig.2.Disconnectthe1700-cm cylinderatEand 10.2.1.2 Analytical Column—9 m by 0.53-mm inside diam-
TM
eter GSQ plus 25 m by 0.53 mm inside diameter PORA-
evacuate. Close Valve B and open Valves C and D, allowing
TM
the liquid sample to flow into the small cylinder. OpenValve B PLOT U (Chrompack).
10.2.2 Injection Mode—Split.
slowlyandallowthesampletoflowthroughuntilasteadyslow
stream of liquid emerges from B. Close Valves B, C, and D in 10.2.3 Split Ratio—At 1:1.
10.2.4 Split Volume—At 15 mL/min.
that order, trapping a portion of the liquid sample in the pipe
cylinder. Attach the evacuated cylinder (1700-cm volume) at 10.2.5 Injection Volume—At 1.00 mL.
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D5507 − 99 (2008)
10.3.1 Equilibrate the GC oven for isothermal operation at
150°C.
10.3.2 With the system operated in the monitor mode (that
is, heart-cut valve open and plunger up), a series of 1.0-mLgas
injections are made with a sample of high-purity vinyl chlo-
ride.Theoutputsfrombothdetectorsshouldbeobservedwhile
these test probes are being made.
10.3.3 Whenthemid-pointpressureissetbelowthebalance
point, splitting of the test peak will occur at the mid-point
restrictor, and responses will be recorded from both detectors.
10.3.4 The mid-point pressure is increased sl
...
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