1、Designation: D 4337 89 (Reapproved 2003)Standard Test Methods forAnalysis of Linear Detergent Alkylates1This standard is issued under the fixed designation D 4337; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last re
2、vision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover chemical and physical testsapplicable to linear detergent alkylates, evaluating those prop-erties w
3、hich characterize linear detergent alkylates with respectto its suitability for desired uses.NOTE 1Linear detergent alkylates comprises linear alkylbenzenesprepared by varying processes of varying linear alkyl chain length. Thealkylate is sulfonated for surfactant use, the largest application being
4、indetergent products. Careful control of linear detergent alkylate character-istics is desired; during sulfonation, variations of the sulfonate can occurthat may result in either desirable or undesirable end-use properties.1.2 The test methods appear as follows:SectionComposition by Gas Chromatograp
5、hy 7-15Chlorides 16-27Color 28-30Refractive Index 31-33Specific Gravity 34-36Water 37-391.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices
6、 and determine the applica-bility of regulatory limitations prior to use. Material SafetyData Sheets are available for reagents and materials. Reviewthem for hazards prior to usage. See also Note 1 and Section21.2. Referenced Documents2.1 ASTM Standards:D 270 Method of Sampling Petroleum and Petrole
7、um Prod-ucts2D 1122 Test Method for Specific Gravity of Engine CoolantConcentrates and Engine Coolants by the Hydrometer3D 1193 Specification for Reagent Water4D 1209 Test Method for Color of Clear Liquids (Platinum-Cobalt Scale)5D 1218 Test Method for Refractive Index and RefractiveDispersion of Hy
8、drocarbon Liquids6D 1364 Test Method for Water in Volatile Solvents (FischerReagent Titration Method)5E 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial Chemicals33. Significance and Use3.1 These test methods are suitable for setting specificationson l
9、inear detergent alkylates and for quality control wherethese alkylates are manufactured or are used in a manufactur-ing process.3.2 The gas chromatography test is useful in identifyinglinear detergent alkylates produced by the various manufactur-ing processes and for determining the applicability of
10、 a lineardetergent alkylate to a particular end use. Test conditions havebeen optimized for resolution of the C-9 to C-15 lineardetergent alkylates and the presence of higher or lower chainlengths will be readily apparent but may produce erroneousresults. The tetralin structures have not been suffic
11、ientlyidentified to allow determination of tetralins, and small uni-dentified components are reported as tetralins and unidenti-fieds.3.3 Some linear detergent alkylates use a manufacturingprocess with an organic chloride as a precursor. This test maybe used to ensure that the chloride content of th
12、e alkylate is notexcessive for a particular end use.3.4 The platinum-cobalt color test is useful in determiningthat the color of the linear detergent alkylate will not contributeto the color of the end use product.3.5 The refractive index and specific gravity tests arepossible aids in the identifica
13、tion of linear detergent alkylatesand in evaluating alkylates for gross contaminants.1These test methods are under the jurisdiction of ASTM Committee D12 onSoaps and other Detergents and are the direct responsibility of SubcommitteeD12.12 on Analysis of Soaps and Synthetic Detergents.Current edition
14、 approved May 26, 1989. Published June 1990. Originallypublished as D 4337 84. Last previous edition D 4337 84a.2Discontinued, see 1984 Annual Book of ASTM Standards, Vol 05.01.3Annual Book of ASTM Standards, Vol 15.05.4Annual Book of ASTM Standards, Vol 11.01.5Annual Book of ASTM Standards, Vol 06.
15、04.6Annual Book of ASTM Standards, Vol 05.01.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.3.6 The water test is suitable for determining that lineardetergent alkylates do not contain amounts of water deleteriousto further processi
16、ng.4. Purity of Reagents4.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,7where such specifications are av
17、ailable. Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.4.2 Unless otherwise indicated, references to water shall beunderstood to mean Type III water conforming to Specifica
18、tionD 1193.5. Precautions5.1 Consult the latest OSHA regulations regarding all re-agents and materials used in these test methods.86. Sampling6.1 Unless otherwise indicated in a specific test method,sample the material in accordance with Method D 270, withspecial application of Sections 41 and 42 pe
19、rtaining to indus-trial aromatic hydrocarbons, Section 12 pertaining to Bottle orBeaker Sampling, and Section 15 pertaining to Tap Sampling.Samples must be taken and stored in amber, screw-cap, glassbottles to protect them from light.COMPOSITION BY GAS CHROMATOGRAPHY7. Scope7.1 The gas chromatograph
20、y test was developed to allowdetermination of C-9 through C-15 linear detergent alkylateisomer distribution before sulfonation. The analyses of stockshaving a chain length distribution above or below the intervalcovered in this test method will require a different set ofoperating conditions. If wate
21、r, extremely high boiling compo-nents, or unusual impurities are present in the linear detergentalkylate, this test would not necessarily detect them and mayproduce erroneous results.8. Summary of Test Method8.1 A sample is injected by means of a microsyringe into avaporization chamber of a gas chro
22、matograph. A stream splitterallows the majority of the sample to be vented into theatmosphere through a valve that is incorporated in the vapor-ization chamber. A small portion of the sample is then swept bythe carrier gas into a capillary column that has been coated witha thin layer of the stationa
23、ry phase. A hydrogen flame ioniza-tion detector provides a very sensitive means of detecting theextremely small concentrations of separated vapor componentsas they elute from the column. An electrometer-amplifierconverts the detector signal into a suitable signal that can berecorded on a standard st
24、rip-chart recorder and integrated by asuitable integration device. The concentrations of the compo-nents are obtained by normalizing the integrated areas, basedon the assumption that all components of the mixture are elutedunder the conditions used.9. Apparatus9.1 Gas Chromatograph, with the followi
25、ng characteristics:9.1.1 Sample Injection Port, operable at 250C and contain-ing a stream splitter capable of linearly splitting sampleinjections up to 1000 to 1.9.1.2 Column Oven, capable of temperature programmingfrom 120 to 165C at a rate of 1 or 2C per min.9.1.3 Flame Ionization Detector, capabl
26、e of operating at300C.9.2 Recorder, 0 to 1 mv range with 0.1 second full scaledeflection.9.3 Integration Device, capable of accurately measuringareas of up to 250 components.9.4 Column, 150 ft (45.7 m) by 0.01 in. (0.25 mm) insidediameter stainless steel wall; open tubular capillary column7Reagent C
27、hemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand Nati
28、onal Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.8Available from Occupational Safety and Health Review Commission, 1825 KStreet, Washington, DC 20006.FIG. 1 Typical Gas Chromatic Scan of an AlkylateD 4337 89 (2003)2coated with phenyl methyl silicone DC-5509or other columnthat
29、 will perform required separation as indicated in Fig. 1.9.5 Syringe, 10-L capacity with fixed 2-in. (5.1 cm)needle.1010. Reagents10.1 Carrier Gas, high-purity nitrogen.10.2 Hydrogen, 99.996 mol % pure.10.3 Compressed Air.11. Calibration11.1 No calibration or correction factors are necessary as ther
30、esponse of the flame ionization detector is essentially constantfor aromatic hydrocarbons. The individual peak area percent-ages may be regarded as the actual weight percent in thesample.12. Procedure12.1 Adjust the chromatograph to the following conditions:Column temperature, C (Note 2) 120 program
31、med to 160 at 1 to 2Cper minInjection port temperature, C 250Detector temperature, C 300Carrier gas pressure, lbf 60Sample size (Note 3), L 0.5 to 1Chart speed, cm/min 1Hydrogen flow (Note 4), mL/min 30Air flow (Note 4), mL/min 240Range X1Attenuator setting X4Splitter (Note 3) 1000/1NOTE 2These cond
32、itions should give adequate separation. It may benecessary to adjust conditions slightly to meet the separation criteria of thesample chromatogram (Fig. 1), depending upon the performance of thecapillary column.NOTE 3Sample size and splitter ratio should be adjusted to obtain apeak height of 10 to 1
33、5 mV for the largest components.NOTE 4Hydrogen and air flows should be adjusted to give maximumdetector sensitivity. See instructions in instrument instruction manual.12.2 When a new column is installed, leak-test the plumb-ing connections by applying the operating carrier gas pressure.The air and h
34、ydrogen connections to the detector should beleak tested periodically. In particular, the hydrogen supplyshould be leak-tested at the cylinder each time the cylinder ischanged, due to the hazardous nature of hydrogen gas.12.3 Wet and rinse the syringe with the sample and draw anexcess of liquid into
35、 the syringe barrel. Exercise caution that allair bubbles are excluded from the liquid in the syringe.Carefully depress the plunger until the exact amount of liquiddesired is contained in the syringe.12.4 Open the split valve and quickly pierce the septum,thrusting the needle of the syringe complete
36、ly into the inlet. Inthe same motion quickly and completely depress the plunger.Immediately withdraw the syringe and start the column oventemperature program sequence. The split valve may be closed1 min after the injection of the sample, but it must always beclosed at exactly the same time after inj
37、ection.12.5 Compare the sample chromatogram with the standardchromatogram (Fig. 1) and from the retention times of thecomponents identify all straight chain alkyl benzene isomers.Label all peaks whose identity has been established. Manyunidentified minor peaks will appear as minor constituents ofthe
38、 sample and may be attributed to tetralin structures. Includethese peaks in the calculations and report in a pooled percent-age as tetralins and unknowns.13. Calculations13.1 Calculate the percentage for each component by divid-ing the area of each component by the total area of allcomponents and mu
39、ltiplying by 100.13.2 Calculate the total 2-phenyl isomer by summing to-gether the 2-phenyl isomers for all chain lengths.13.3 Calculate the chain length distribution by summingtogether all percentages for the identified linear alkyl benzeneisomers of each chain length.13.4 Calculate lights (compone
40、nts eluting before C10alkylbenzene) by summing together the percentages of all thecomponents eluting before 5-phenyldecane.13.5 Calculate heavies (components eluting after C14alkylbenzene) by summing together all the percentages of thecomponents eluting after 2-phenyltetradecane.13.6 Calculate tetra
41、lins and unknowns by summing togetherthe percentages of all unidentified peaks eluting between the5-phenyldecane peak and the 2-phenyltetradecane peak.13.7 Determine the average molecular weight by assumingthe tetralins and unknowns to have a molecular weight of 244.The average molecular weight is c
42、alculated to the third decimalplace using the following equation:Average molecular weight 5 100 2lights (1)1 heavies!#/( C10isomers/218!1 ( C11isomers/232! 1 ( C12isomers/246!1 ( C13isomers/260! 1 ( C14isomers/274!1 ( tetralins 1 unknowns/244!#14. Report14.1 Report the components and average molecul
43、ar weightas specified in Table 1. Duplicate runs that agree within thechecking limits shown in Table 1 are acceptable for averaging(95 % confidence level).15. Precision and Bias15.1 The following criteria should be used for judging theacceptability of results:15.1.1 Repeatability (Single Analyst) Th
44、e standard devia-tion of results (each the average of duplicates), obtained by thesame analyst on different days, has been estimated to be thevalue shown in Table 1 with the indicated degrees of freedom.Two such results should be considered suspect (95 % confi-dence level) if they differ by more tha
45、n the values in Table 1.15.1.2 Reproducibility (Multilaboratory) The standarddeviation of results (each the average of duplicates), obtainedby analysts in different laboratories, has been estimated to be9Capillary column, Part 009-0354, available from Perkin-Elmer Corporation,Norwalk, CT, has been f
46、ound satisfactory.10Microsyringe No. 701, available from Hamilton Co., P. O. Box 307, Whittier,CA, has been found satisfactory.D 4337 89 (2003)3the value shown in Table 1 with the indicated degrees offreedom. Two such results should be considered suspect (95 %confidence level) if they differ by more
47、 than the values shownin Table 1 (Note 5).NOTE 5The preceding precision estimates are based on an interlabo-ratory study of six samples of linear detergent alkylates. A total of eightlaboratories cooperated in the studies in which duplicate determinationswere performed on each of 2 days. Practice E
48、180 was used in developingthese precision estimates.ORGANIC CHLORIDES16. Scope16.1 This test method is suitable for the rapid determinationof organic chlorides in linear detergent alkylates before sul-fonation. The test method is applicable to samples whichinclude chloride-containing compounds that
49、are volatile at700C. Compounds such as sodium chloride do not completelyvolatilize under the operating conditions specified and are notquantified. By using the proper sample size, this test method isapplicable to the direct detection of chlorides at levels up to700 ppm. Halogen compounds other than those containingchlorides tend to be nonquantitatively detected by this method.17. Summary of Test Method17.1 Liquid samples are injected into a flowing stream ofgas containing about 80 % oxygen and 20 % inert gas such asnitrogen, helium or argon. The gas and
