1、Designation: D3712 05 (Reapproved 2017)Designation: 369/(95)Standard Test Method ofAnalysis of Oil-Soluble Petroleum Sulfonates by LiquidChromatography1This standard is issued under the fixed designation D3712; the number immediately following the designation indicates the year oforiginal adoption o
2、r, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the analysis of refined and crudenatural and synthetic
3、 oil-soluble sulfonate products. Resins, ifpresent, are recovered with the oil phase and carboxylates arerecovered as sulfonates.1.2 This test method covers the determination of mineraloil, sodium sulfonate, inorganic salts, water, basicity or acidity,average molecular weight, and relative density o
4、f sodiumsulfonate products.1.3 This test method covers the determination of mineraloil, sulfonate, water, base number, average molecular weight,and relative density of calcium, barium, magnesium, andammonium sulfonate products.1.4 The values stated in SI units are to be regarded as thestandard.1.4.1
5、 ExceptionThe values given in parentheses are forinformation only.1.5 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 and determine the app
6、lica-bility of regulatory limitations prior to use.1.6 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued b
7、y the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D95 Test Method for Water in Petroleum Products andBituminous Materials by DistillationD2896 Test Method for Base Number of Petroleum Productsby Potentiometric Perchloric Acid Titrati
8、on3. Terminology3.1 Symbols:3.1.1 Following are definitions of the symbols used inSection 17, and as noted in the sections in parentheses.A = grams of sample of calcium, barium, magnesium, or ammoniumsulfonate (8.1.1).B = volume of chloroform solution, mL (10.1).C = grams of sample of sodium sulfona
9、te (10.1.1).D = grams of oil recovered (10.4).E = grams of sodium sulfonate recovered (10.5).F = grams of residue from chloroform blank (10.6).G = grams of residue from alcohol blank (10.6).H = grams of sodium sulfonate (11.1).I = grams of sodium sulfate ash from sodium sulfonate (11.2).J = T/KS.K =
10、 valence of cation.S = average equivalent weight of sodium sulfonate (17.1.4).T = average molecular weight of calcium, barium, magnesium, orammonium sulfonate (17.1.5).U = percentage of sodium sulfonate (17.1.2).V = percentage of calcium, barium, magnesium, or ammoniumsulfonate (17.1.3).Wc= grams of
11、 water contained in pycnometer at 25 C (6.9).Ws= grams of sample contained in pycnometer at 25 C (15.1).X = grams of sodium sulfonate sample for basicity (12.1).Y = volume of standard H2SO4or NaOH solution used to determinebasicity or acidity (12.1).Z = normality of standard H2SO4or NaOH solution to
12、 determine freebasicity or acidity (12.1).AA = grams of sodium sulfonate product ashed (13.1).BB = grams of sodium sulfate from inorganic salt determination (13.1).1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricantsand is the direct re
13、sponsibility ofSubcommittee D02.04.0C on Liquid Chromatography.Current edition approved July 15, 2017. Published July 2017. Originallyapproved in 1978. Last previous edition approved in 2011 as D3712 05 (2011).DOI: 10.1520/D3712-05R17.This test method was adopted as a joint ASTM-IP standard.2For ref
14、erenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, Wes
15、t Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Tr
16、ade Organization Technical Barriers to Trade (TBT) Committee.1CCA= percentage of free acidity of sodium sulfonate product as H2SO4(17.1.6).CCB= percentage of free basicity of sodium sulfonate product as NaOH(17.1.6).DD = percentage of inorganic salts as sodium sulfate (17.1.7).4. Summary of Test Met
17、hod4.1 The sample, except a sodium sulfonate product, isdissolved in ethyl ether and converted to sulfonic acid, usingdilute hydrochloric acid. The sulfonic acid after extraction isconverted to sodium sulfonate and the isolated sodium sul-fonate and mineral oil are dissolved in chloroform. An aliquo
18、tof the chloroform solution, or a sample of a sodium sulfonateproduct, dissolved in chloroform, is placed on a silica gelcolumn. The oil is eluted with chloroform, the sulfonate withethyl alcohol, and both are determined gravimetrically. Aver-age molecular weight is calculated from the average equiv
19、alentweight of the sodium sulfonate, which is determined by ashinga portion of the isolated sodium sulfonate.4.2 Water is determined by Test Method D95. Base numberis determined by Test Method D2896. Relative density isdetermined by pycnometer.5. Significance and Use5.1 This test method provides a m
20、eans of determiningsulfonate content and of classifying and characterizing naturaland synthetic petroleum sulfonate products by sulfonate con-tent and average molecular weight. Purity of sodium sulfonateproducts is measured by basicity and inorganic salt contentsand the reserve alkalinity of alkalin
21、e earth sulfonates by thetotal base number.6. Apparatus6.1 Chromatographic column, made of glass and consistingof a reservoir and separator section, and fitted with a TFE-fluorocarbon stopcock with a 2 mm bore, as shown in Fig. 1.Acolumn with a detachable reservoir connected by a standard-taper join
22、t can be used.6.2 Steam Bath.6.3 Vacuum Desiccator, shielded.6.4 Vacuum Oven, capable of being maintained at 100 C(212 F) and connected to 559 mm to 635 mm (22 in. to 29 in.)Hg vacuum.6.5 Muffle Furnace, capable of operating at 800 C to1000 C (1500 F to 1800 F).6.6 Dish, platinum, 100 mL capacity.6.
23、7 Distillation Apparatus, as described in Test MethodD95.6.8 Water Bath, capable of being maintained at 25 C 60.2 C (77 F 6 0.3 F).6.9 Pycnometer, as shown in Fig. 2. To calibrate, weigh tothe nearest 1 mg with cap in place; then fill with distilled waterat 15 C to 20 C (60 F to 68 F) and place in w
24、ater bath at25 C 6 0.2 C (77 F 6 0.3 F). After 30 min, adjust thewater meniscus at the top of the neck so it is exactly level. Toobtain a flat meniscus, add a minute amount of wetting agent tothe water surface. Remove the pycnometer from the bath, anddry the outside. Replace the cap and weigh to the
25、 nearest 1 mg.Record the mass of water contained as Wc.7. Reagents and Materials7.1 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 Ame
26、rican Chemical Society,FIG. 1 Chromatographic ColumnFIG. 2 Pycnometer for Determining Relative Density ofPetroleum SulfonatesD3712 05 (2017)2where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its
27、 use without lessening theaccuracy of the determination.7.2 Chloroform (WarningFlammable, Health Hazard.).7.3 Ethyl Alcohol (95 %) Either pure grain or denaturedethyl alcohol conforming to Formula 3A of the U.S. Bureau ofInternal Revenue (WarningFlammable. Denatured alcoholcannot be made nontoxic.).
28、7.4 Ethyl Ether (WarningExtremely flammable. Harmfulif inhaled. May cause eye injury. Effects may be delayed. Mayform explosive peroxides. Vapors may cause flash fire. Mod-erately toxic. Irritating to skin.).7.5 Filter Paper, slow-filtering, ashless, gravimetric.7.6 Hydrochloric Acid (Concentrated)(
29、WarningPoison. Corrosive. May be fatal if swallowed. Liquid andvapor cause severe burns. Harmful if inhaled.).7.6.1 Hydrochloric Acid, Dilute (1 + 1) (See Warning in7.6.) One volume of concentrated hydrochloric acid (HCl) isadded to 1 volume of water.7.6.2 Hydrochloric Acid, Dilute (1 + 3) (See Warn
30、ing in7.6.) One volume of concentrated hydrochloric acid (HCl) isadded to 3 volumes of water.7.7 Isopropyl Alcohol (99 % by Mass)Water content shallbe 0.9 % by mass maximum. (WarningFlammable.)7.7.1 Isopropyl Alcohol, Dilute (1+1) One volume of99 % by mass isopropyl alcohol is diluted with 1 volume
31、ofwater.7.8 Methyl Orange Indicator SolutionDissolve 1.0 g ofmethyl orange in water and dilute to 1 L.7.9 Phenolphthalein Indicator SolutionDissolve 1 g ofphenolphthalein in 100 mL of 50% by mass ethyl alcohol.7.10 Silica Gel, 250 m to 74 m (60 mesh to 200 mesh).47.11 Sodium Hydroxide Solution, Stan
32、dard (0.1 molL)(WarningCorrosive. Can cause severe burns or blindness.Evolution of heat produces a violent reaction or eruption upontoo rapid mixture with water.)Prepare and standardize a0.1 molL aqueous, carbonate-free, NaOH solution.7.12 Sodium Sulfate, Anhydrous, Crystalline.7.13 Sodium Sulfate S
33、olutionDissolve 240 g of sodiumsulfate (Na2SO4) in water and dilute to 1 L.7.14 Sulfuric Acid (relative density 1.84)Concentratedsulfuric acid (H2SO4), 36 molL. (WarningPoison. Corro-sive. Strong oxidizer. Contact with organic material may causefire. May be fatal if swallowed. Liquid and vapor cause
34、 severeburns. Harmful if inhaled. Contact with water liberates largeamounts of heat. Spillage may cause fire.7.14.1 Sulfuric Acid Solution, Standard (0.1 molL)Prepare and standardize a 0.1 molL aqueous sulfuric acid(H2SO4).8. Conversion of Calcium, Barium, Magnesium, orAmmonium Sulfonate to Sodium S
35、ulfonate8.1 Conversion of Calcium, Barium, Magnesium or Ammo-nium Sulfonate to Sulfonic Acid:8.1.1 Transfer approximately 10 g of sample, weighed to thenearest 0.001 g into a 250 mL Erlenmeyer flask, designatingthis weight as A. Add 50 mL of ethyl ether and stir to dissolvethe sample.Add 100 mL of d
36、ilute HCl (1 + 1) and swirl to mixthoroughly until reaction is complete. In analyzing bariumsulfonate products if barium chloride crystallizes out, addsufficient water to redissolve.8.1.2 Quantitatively transfer the mixture to a 500 mL sepa-ratory funnel. Shake well, let settle, and draw the aqueous
37、 acidlayer into a 250 mLseparatory funnel. Extract the aqueous acidlayer in the 250 mL separatory funnel with three 50 mLportions of ethyl ether, using the ethyl ether washes to rinse theErlenmeyer flask first. Combine all the ethyl ether extracts inthe 500 mL separatory funnel and wash with 50 mL o
38、f diluteHCl (1 + 3). Combine all the aqueous acid layers and reextractthem with 50 mL of ethyl ether.8.2 Conversion of Sulfonic Acid to Sodium Sulfonate:8.2.1 Collect all of the ether washes in the 500 mL separa-tory funnel and shake with successive 50 mL portions ofNa2SO4solution containing 2 to 3
39、drops of methyl orangeindicator until a washing does not appear pink. Discard the saltwashes.8.2.2 Drain off as much of the aqueous layer as possiblefrom the washed ether solution. Lay the separatory funnel onits side and introduce about 10 g of anhydrous Na2SO4.Stopper the funnel, making sure that
40、the funnel mouth is free ofNa2SO4crystals and shake the mixture vigorously for 3 min to4 min, to remove the last traces of water, venting the funnelfrequently. Place a 250 mL Erlenmeyer flask on a steam bathand filter the ether solution through a small plug of cotton,placed in the vortex of a filter
41、 funnel, into the Erlenmeyer flask,keeping approximately 50 mL of solution in the Erlenmeyerflask while evaporating. Rinse the funnel and filter with 50 mLof ethyl ether, adding the rinsing to the main ether solution.Evaporate the ethyl ether until approximately 10 mL of solu-tion remains. Add 50 mL
42、 of 99 % by mass isopropyl alcohol,several drops of phenolphthalein indicator solution, and titratewith 0.1 molL standard NaOH solution to the red colorchange. Place the flask on a steam bath and evaporate todryness. Dissolve the sodium sulfonate and oil residue inchloroform; transfer quantitatively
43、 into a 100 mL volumetricflask, adjust to volume, and proceed directly with Section 10.The solution may turn acidic on standing in the laboratory.Should this occur, add sufficient 0.1 N NaOH solution to thealiquot taken until the solution is pink.3Reagent Chemicals, American Chemical Society Specifi
44、cations, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Conventi
45、on, Inc. (USPC), Rockville,MD.4The sole source of supply of silica gel, Grade 62, known to the committee atthis time is W.R. Grace and Co., Davison Chemical Corp., Baltimore, MD 21203.If you are aware of alternative suppliers, please provide this information to ASTMInternational Headquarters. Your c
46、omments will receive careful consideration at ameeting of the responsible technical committee,1which you may attend.D3712 05 (2017)39. Preparation of the Column9.1 With the stopcock closed, pour 80 mL to 100 mL ofchloroform into the column, and push a wad of cotton to thebottom with a rod (Note 1).
47、Compress the cotton enough tohold back the silica gel but not enough to impede the flow ofsolvent.NOTE 1Acoarse-fritted disk made of borosilicate glass can be used inplace of the cotton wad.9.2 Pour 15 g 6 1 g of silica gel into the column containingthe chloroform. The column must be free of air bub
48、bles toavoid channeling. Start the flow of chloroform by opening thestopcock. When the liquid level is within 13 mm (12 in.) of thesurface of the gel, close the stopcock. Never allow the liquidlevel to fall below the surface of the silica gel.10. Separation of Mineral Oil and Sodium Sulfonate10.1 Ad
49、sorption of the SampleTransfer a sufficient quan-tity of the chloroform solution of sodium sulfonate and mineraloil to provide approximately 1.25 g of Na2SO4(8.2.2) onto thecolumn, being careful to prevent channeling. Designate thevolume as B. Use the following information as a guide inselecting the appropriate volume of sample:Approximate Sulfonate Content of Product Volume ofAliquot20 % 75 mL30 % 50 mLAbove 40 % 25 mL10.1.1 For Sodium Sulfonate ProductsTransfer approxi-mately 2 g of sample, weighed to the nearest 0.001 g, into
