1、Designation: D3712 05 (Reapproved 2017)D3712 18Designation: 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 ad
2、option or, 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. Scope Scope*1.1 This test method covers the analysis of refined and crude natur
3、al and synthetic oil-soluble sulfonate products. Resins, ifpresent, are recovered with the oil phase and carboxylates are recovered as sulfonates.1.2 This test method covers the determination of mineral oil, sodium sulfonate, inorganic salts, water, basicity or acidity,average molecular weight, and
4、relative density of sodium sulfonate products.1.3 This test method covers the determination of mineral oil, sulfonate, water, base number, average molecular weight, andrelative density of calcium, barium, magnesium, and ammonium sulfonate products.1.4 The values stated in SI units are to be regarded
5、 as the standard. standard. The values given in parentheses after SI units areprovided for information only and are not considered standard.1.4.1 ExceptionThe values given in parentheses are for information only.1.5 This standard does not purport to address all of the safety concerns, if any, associ
6、ated with its use. It is the responsibilityof the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine theapplicability of regulatory limitations prior to use.1.6 This international standard was developed in accordance with internation
7、ally recognized principles on standardizationestablished in the Decision on Principles for the Development of International Standards, Guides and Recommendations issuedby the World Trade Organization Technical Barriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D95 Test Meth
8、od for Water in Petroleum Products and Bituminous Materials by DistillationD2896 Test Method for Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration3. Terminology3.1 Symbols:3.1.1 Following are definitions of the symbols used in Section 17, and as noted in the sections in p
9、arentheses.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 recovered (10.4).E = grams of sodium sulfonate recovered (10.5).F = grams of residue from chlorofo
10、rm 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).1 This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricantsand is the direct resp
11、onsibility of SubcommitteeD02.04.0C on Liquid Chromatography.Current edition approved July 15, 2017April 1, 2018. Published July 2017May 2018. Originally approved in 1978. Last previous edition approved in 20112017 asD3712 05 (2011).(2017). DOI: 10.1520/D3712-05R17.10.1520/D3712-18.This test method
12、was adopted as a joint ASTM-IP standard.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.This document is not
13、an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate.
14、 In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1J =
15、T/KS.K = 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 =
16、 grams of 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 H2SO4 or NaOH solution used to determinebasicity or acidity (12.1).Z = normality of standard H2SO4 or NaOH
17、 solution to 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).CCA = percentage of free acidity of sodium sulfonate product as H2SO4(17.1.6).CCB = percentage of free basicity of sodium su
18、lfonate product as NaOH(17.1.6).DD = percentage of inorganic salts as sodium sulfate (17.1.7).4. Summary of Test Method4.1 The sample, except a sodium sulfonate product, is dissolved in ethyl ether and converted to sulfonic acid, using dilutehydrochloric acid.The sulfonic acid after extraction is co
19、nverted to sodium sulfonate and the isolated sodium sulfonate and mineraloil are dissolved in chloroform. An aliquot of the chloroform solution, or a sample of a sodium sulfonate product, dissolved inchloroform, is placed on a silica gel column. The oil is eluted with chloroform, the sulfonate with
20、ethyl alcohol, and both aredetermined gravimetrically. Average molecular weight is calculated from the average equivalent weight of the sodium sulfonate,which is determined by ashing a portion of the isolated sodium sulfonate.4.2 Water is determined byTest Method D95. Base number is determined byTes
21、t Method D2896. Relative density is determinedby pycnometer.5. Significance and Use5.1 This test method provides a means of determining sulfonate content and of classifying and characterizing natural andsynthetic petroleum sulfonate products by sulfonate content and average molecular weight. Purity
22、of sodium sulfonate productsis measured by basicity and inorganic salt contents and the reserve alkalinity of alkaline earth sulfonates by the total base number.6. Apparatus6.1 Chromatographic column, made of glass and consisting of a reservoir and separator section, and fitted with aTFE-fluorocarbo
23、n stopcock with a 2 mm bore, as shown in Fig. 1. A column with a detachable reservoir connected by astandard-taper joint 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.) Hgvac
24、uum.6.5 Muffle Furnace, capable of operating at 800 C to 1000 C (1500 F to 1800 F).6.6 Dish, platinum, 100 mL capacity.6.7 Distillation Apparatus, as described in Test Method D95.6.8 Water Bath, capable of being maintained at 25 C 6 0.2 C (77 F 6 0.3 F).6.9 Pycnometer, as shown in Fig. 2. To calibra
25、te, weigh to the nearest 1 mg with cap in place; then fill with distilled water at15 C to 20 C (60 F to 68 F) and place in water bath at 25 C60.2 C (77 F60.3 F).After 30 min, adjust the water meniscusat the top of the neck so it is exactly level. To obtain a flat meniscus, add a minute amount of wet
26、ting agent to the water surface.Remove the pycnometer from the bath, and dry the outside. Replace the cap and weigh to the nearest 1 mg. Record the mass ofwater contained as Wc.7. Reagents and Materials7.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicat
27、ed, it is intended that allreagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, whereD3712 182such specifications are available.3 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently highpurit
28、y to permit its use without lessening the accuracy of the determination.7.2 Chloroform (WarningFlammable, Health Hazard.).7.3 Ethyl Alcohol (95 %) Either pure grain or denatured ethyl alcohol conforming to Formula 3A of the U.S. Bureau ofInternal Revenue (WarningFlammable. Denatured alcohol cannot b
29、e made nontoxic.).7.4 Ethyl Ether (WarningExtremely flammable. Harmful if inhaled. May cause eye injury. Effects may be delayed. May formexplosive peroxides. Vapors may cause flash fire. Moderately toxic. Irritating to skin.).3 Reagent Chemicals, American Chemical Society Specifications, American Ch
30、emical Society, Washington, DC. For Suggestions on the testing of reagents not listed bythe American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), R
31、ockville, MD.FIG. 1 Chromatographic ColumnFIG. 2 Pycnometer for Determining Relative Density ofPetroleum SulfonatesD3712 1837.5 Filter Paper, slow-filtering, ashless, gravimetric.7.6 Hydrochloric Acid (Concentrated)(WarningPoison. Corrosive. May be fatal if swallowed. Liquid and vapor causesevere bu
32、rns. Harmful if inhaled.).7.6.1 Hydrochloric Acid, Dilute (1 + 1) (See Warning in 7.6.) One volume of concentrated hydrochloric acid (HCl) is addedto 1 volume of water.7.6.2 Hydrochloric Acid, Dilute (1 + 3) (See Warning in 7.6.) One volume of concentrated hydrochloric acid (HCl) is addedto 3 volume
33、s of water.7.7 Isopropyl Alcohol (99 % by Mass)Water content shall be 0.9 % by mass maximum. (WarningFlammable.)7.7.1 Isopropyl Alcohol, Dilute (1 + 1) One volume of 99 % by mass isopropyl alcohol is diluted with 1 volume of water.7.8 Methyl Orange Indicator SolutionDissolve 1.0 g of methyl orange i
34、n water and dilute to 1 L.7.9 Phenolphthalein Indicator SolutionDissolve 1 g of phenolphthalein 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, Standard (0.1 molL) (WarningCorrosive. Can cause severe burns or blindness. Evo
35、lutionof heat produces a violent reaction or eruption upon too rapid mixture with water.)Prepare and standardize a 0.1 molL aqueous,carbonate-free, NaOH solution.7.12 Sodium Sulfate, Anhydrous, Crystalline.7.13 Sodium Sulfate SolutionDissolve 240 g of sodium sulfate (Na2SO4) in water and dilute to 1
36、 L.7.14 Sulfuric Acid (relative density 1.84)Concentrated sulfuric acid (H2SO4), 36 molL. (WarningPoison. Corrosive.Strong oxidizer. Contact with organic material may cause fire. May be fatal if swallowed. Liquid and vapor cause severe burns.Harmful if inhaled. Contact with water liberates large amo
37、unts 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, or Ammonium Sulfonate to Sodium Sulfonate8.1 Conversion of Calcium, Barium, Magnesium or Ammonium Sulf
38、onate to Sulfonic Acid:8.1.1 Transfer approximately 10 g of sample, weighed to the nearest 0.001 g into a 250 mL Erlenmeyer flask, designating thisweight as A. Add 50 mL of ethyl ether and stir to dissolve the sample. Add 100 mL of dilute HCl (1 + 1) and swirl to mixthoroughly until reaction is comp
39、lete. In analyzing barium sulfonate products if barium chloride crystallizes out, add sufficientwater to redissolve.8.1.2 Quantitatively transfer the mixture to a 500 mL separatory funnel. Shake well, let settle, and draw the aqueous acid layerinto a 250 mLseparatory funnel. Extract the aqueous acid
40、 layer in the 250 mLseparatory funnel with three 50 mLportions of ethylether, using the ethyl ether washes to rinse the Erlenmeyer flask first. Combine all the ethyl ether extracts in the 500 mLseparatoryfunnel and wash with 50 mL of dilute HCl (1 + 3). Combine all the aqueous acid layers and reextr
41、act them with 50 mL of ethylether.8.2 Conversion of Sulfonic Acid to Sodium Sulfonate:8.2.1 Collect all of the ether washes in the 500 mL separatory funnel and shake with successive 50 mL portions of Na2SO4solution containing 2 to 3 drops of methyl orange indicator until a washing does not appear pi
42、nk. Discard the salt washes.8.2.2 Drain off as much of the aqueous layer as possible from the washed ether solution. Lay the separatory funnel on its sideand introduce about 10 g of anhydrous Na2SO4. Stopper the funnel, making sure that the funnel mouth is free of Na2SO4 crystalsand shake the mixtur
43、e vigorously for 3 min to 4 min, to remove the last traces of water, venting the funnel frequently. Place a250 mLErlenmeyer flask on a steam bath and filter the ether solution through a small plug of cotton, placed in the vortex of a filterfunnel, into the Erlenmeyer flask, keeping approximately 50
44、mL of solution in the Erlenmeyer flask while evaporating. Rinse thefunnel and filter with 50 mL of ethyl ether, adding the rinsing to the main ether solution. Evaporate the ethyl ether untilapproximately 10 mL of solution remains. Add 50 mL of 99 % by mass isopropyl alcohol, several drops of phenolp
45、hthaleinindicator solution, and titrate with 0.1 molL standard NaOH solution to the red color change. Place the flask on a steam bath andevaporate to dryness. Dissolve the sodium sulfonate and oil residue in chloroform; transfer quantitatively into a 100 mLvolumetricflask, adjust to volume, and proc
46、eed directly with Section 10. The solution may turn acidic on standing in the laboratory. Shouldthis occur, add sufficient 0.1 N NaOH solution to the aliquot taken until the solution is pink.9. Preparation of the Column9.1 With the stopcock closed, pour 80 mL to 100 mL of chloroform into the column,
47、 and push a wad of cotton to the bottomwith a rod (Note 1). Compress the cotton enough to hold back the silica gel but not enough to impede the flow of solvent.4 The sole source of supply of silica gel, Grade 62, known to the committee at this time is W.R. Grace and Co., Davison Chemical Corp., Balt
48、imore, MD 21203. If youare aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting ofthe responsible technical committee,1 which you may attend.D3712 184NOTE 1A coarse-fritted disk made of boros
49、ilicate glass can be used in place of the cotton wad.9.2 Pour 15 g 6 1 g of silica gel into the column containing the chloroform. The column must be free of air bubbles to avoidchanneling. Start the flow of chloroform by opening the stopcock. When the liquid level is within 13 mm (12 in.) of the surfaceof the gel, close the stopcock. Never allow the liquid level to fall below the surface of the silica gel.10. Separation of Mineral Oil and Sodium Sulfonate10.1 Adsorption of the SampleTransfer a sufficient quantity of the chlor
