1、Designation: D3712 05 (Reapproved 2011)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. The
5、values given in parentheses are for informationonly.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 applica-bility of
6、 regulatory limitations prior to use.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 Prod-ucts by Potentiometric Perchloric Acid Titration3. Terminology3.1 Symbols:3.1.1 F
7、ollowing 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 sulfonate (10.1.1).D = grams of oil recove
8、red (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 = valence of cation.S = average equi
9、valent weight of sodium sulfonate (17.1.4).T = average molecular weight of calcium, barium, magnesium, or am-monium sulfonate (17.1.5).U = percentage of sodium sulfonate (17.1.2).V = percentage of calcium, barium, magnesium, or ammonium sul-fonate (17.1.3).Wc= grams of water contained in pycnometer
10、at 25C (6.9).Ws= grams of sample contained in pycnometer at 25C (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 determine freebasicity or acidit
11、y (12.1).AA = grams of sodium sulfonate product ashed (13.1).BB = grams of sodium sulfate from inorganic salt determination (13.1).CCA= percentage of free acidity of sodium sulfonate product asH2SO4(17.1.6).CCB= percentage of free basicity of sodium sulfonate product as NaOH(17.1.6).DD = percentage
12、of inorganic salts as sodium sulfate (17.1.7).4. Summary of Test Method4.1 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 sodi
13、um sul-fonate and mineral oil are dissolved in chloroform. An aliquotof 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 gravimetric
14、ally. Aver-age molecular weight is calculated from the average equivalentweight of the sodium sulfonate, which is determined by ashinga portion of the isolated sodium sulfonate.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct res
15、ponsibility of SubcommitteeD02.04.0C on Liquid Chromatography.Current edition approved Jan. 1, 2011. Published February 2011. Originallyapproved in 1978. Last previous edition approved in 2005 as D3712 05. DOI:10.1520/D3712-05R11.This test method was adopted as a joint ASTM-IP standard.2For referenc
16、ed 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.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Co
17、nshohocken, PA 19428-2959, United States.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 means of determiningsulfonate content and of classifying and characte
18、rizing 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 alkaline earth sulfonates by thetotal base number.6. Apparatus6.1 Chromatog
19、raphic 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 joint can be used.6.2 Steam Bath.6.3 Vacuum Desiccator, shielded.6.4 Vac
20、uum Oven, capable of being maintained at 100C(212F) and connected to 559 to 635 mm (22 to 29 in.) Hgvacuum.6.5 Muffle Furnace, capable of operating at 800 to 1000C(1500 to 1800F).6.6 Dish, platinum, 100-mL capacity.6.7 Distillation Apparatus, as described in Test MethodD95.6.8 Water Bath, capable of
21、 being maintained at 25 6 0.2C(77 6 0.3F).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 to 20C (60 to 68F) and place in water bath at 25 60.2C (77 6 0.3F).After 30 min, adjust the water meniscus atthe top of the neck
22、 so it is exactly level. To obtain a flatmeniscus, add a minute amount of wetting agent to the watersurface. Remove the pycnometer from the bath, and dry theoutside. Replace the cap and weigh to the nearest 1 mg. Recordthe mass of water contained as Wc.7. Reagents and Materials7.1 Purity of Reagents
23、Reagent 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,where such specifications are available.3Other grades may beused, provided it i
24、s first ascertained that the reagent is ofsufficiently high purity to permit its 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 of
25、Internal Revenue (WarningFlammable. Denatured alcoholcannot be made nontoxic.).7.4 Ethyl Ether (WarningExtremely flammable. Harm-ful if inhaled. May cause eye injury. Effects may be delayed.May form explosive peroxides. Vapors may cause flash fire.Moderately toxic. Irritating to skin.).7.5 Filter Pa
26、per, slow-filtering, ashless, gravimetric.7.6 Hydrochloric Acid (Concentrated)(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)
27、isadded to 1 volume of water.3Reagent Chemicals, American Chemical Society Specifications, 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
28、 the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.FIG. 1 Chromatographic ColumnFIG. 2 Pycnometer for Determining Relative Density ofPetroleum SulfonatesD3712 05 (2011)27.6.2 Hydrochloric Acid, Dilute (1 + 3)(See Warning in7.6.) One volume
29、 of concentrated hydrochloric acid (HCl) isadded to 3 volumes of water.7.7 Isopropyl Alcohol (99 Mass %)Water content shall be0.9 mass % maximum. (WarningFlammable.)7.7.1 Isopropyl Alcohol, Dilute (1 + 1)One volume of 99mass % isopropyl alcohol is diluted with 1 volume of water.7.8 Methyl Orange Ind
30、icator SolutionDissolve 1.0 g ofmethyl orange in water and dilute to 1 L.7.9 Phenolphthalein Indicator SolutionDissolve1gofphenolphthalein in 100 mL of 50 mass % ethyl alcohol.7.10 Silica Gel, 250 to 74 m (60 to 200-mesh).47.11 Sodium Hydroxide Solution, Standard (0.1 mol/L)(WarningCorrosive. Can ca
31、use severe burns or blindness.Evolution of heat produces a violent reaction or eruption upontoo rapid mixture with water.)Prepare and standardize a 0.1mol/L aqueous, carbonate-free, NaOH solution.7.12 Sodium Sulfate, Anhydrous, Crystalline.7.13 Sodium Sulfate SolutionDissolve 240 g of sodiumsulfate
32、(Na2SO4) in water and dilute to 1 L.7.14 Sulfuric Acid (relative density 1.84)Concentratedsulfuric acid (H2SO4), 36 mol/L. (WarningPoison. Corro-sive. Strong oxidizer. Contact with organic material may causefire. May be fatal if swallowed. Liquid and vapor cause severeburns. Harmful if inhaled. Cont
33、act with water liberates largeamounts of heat. Spillage may cause fire.7.14.1 Sulfuric Acid Solution, Standard (0.1 mol/L)Prepare and standardize a 0.1 mol/L aqueous sulfuric acid(H2SO4).8. Conversion of Calcium, Barium, Magnesium, orAmmonium Sulfonate to Sodium Sulfonate8.1 Conversion of Calcium, B
34、arium, 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 dilute HCl (1 + 1) and swirl to mixth
35、oroughly 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 acidlayer into a 250-mLseparatory f
36、unnel. 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 of diluteHCl (1 + 3). Combine all the
37、 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 drops of methyl orangeindicator unti
38、l 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 the funnel mouth is free ofNa2SO4cry
39、stals and shake the mixture vigorously for 3 to 4min, 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 funnel, into the Erlenmeyer flask,keepi
40、ng 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 ofsolution remains. Add 50 mL of 99 mass % isopropyl alcohol,several dr
41、ops of phenolphthalein indicator solution, and titratewith 0.1 mol/L 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 into a 100-mL volumetricflask, adjust to vo
42、lume, 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.9. Preparation of the Column9.1 With the stopcock closed, pour 80 to 100 mL ofchloroform into the
43、 column, and push a wad of cotton to thebottom with a rod (Note 1). 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 6 1 g of silica gel into the c
44、olumn containingthe chloroform. The column must be free of air bubbles 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 si
45、lica gel.10. Separation of Mineral Oil and Sodium Sulfonate10.1 Adsorption 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 thevol
46、ume 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-mately2gofsample, weighed to the nearest 0.001 g, into a10
47、0-mL beaker, designating this weight as C.Add 10 to 25 mLof chloroform and stir to dissolve the sample. Pour the solutiononto the column, being careful to prevent channeling. Rinse the4The sole source of supply of silica gel, Grade 62, known to the committee atthis time is W.R. Grace and Co., Daviso
48、n Chemical Corp., Baltimore, MD 21203.If you are aware of alternative suppliers, please provide this information to ASTMInternational Headquarters. Your comments will receive careful consideration at ameeting of the responsible technical committee,1which you may attend.D3712 05 (2011)3beaker several
49、 times with small portions of chloroform and addthe rinses to the column.10.2 Elution of the Mineral OilTare a 250-mL beaker, tothe nearest 0.0001 g and place it under the column. Open thestopcock and adjust the flow rate to between 1 and 5 drops persecond. Maintain the flow rate throughout the elution of the oiland sulfonate.10.2.1 When the liquid level is within 13 mm (12 in.) of thesurface of the gel, rinse the sides of the column with 10 mL ofchloroform. When the liquid level is again within 13 mm (12in.) of the surface of the gel, add 2
