his internatona landed ae Designation: D974 - 14°? Designation: 139/98 Standard Test Method for lope in secordance with nereainallyeecopsdprncpe tnd nourds, olde and Remedios ued by oe Word rode Ongaiation Tec Datir to Trae (7) Casa, le esos on Prine for the Acid and Base Number by Color-Indicator Titration’ This standard is haued under the ed designtin DOTS; he suber immediatly falling the exgton nets the yer of ginal adogion cr, athe cate of evson, ke year of lt evs, Acumen pnts incetes the year lst approval A ‘Suprseit eala() lates oct ange ince the at rvison or eperova. Tis sand has ben approved for ws by agence ofthe US. Department of Defense ‘FNOTE—Subecion 76 was erected ediorliy a Angus 015, ® NOTESobsestios ‘hand 15.1.2 were comested etry i Febracy 2016 1, Scope* 1.1 This test method covers the determination of acidic or basic constituents (Note 1) in petroleum products® and lubri- canis soluble or nearly soluble in mixsres of toluene and isopropyl alcool. Iti applicable fo the determination of acids for bases whose dissociation constants in water are larger than 10”; extremely weak acids or bases whose dissociation ‘constants are smaller than 10°? do not interfere. Salts react if their hydrolysis constants are larger than 10 ere Ser ete eaee ee eee ee Seca et a pane cael ent aren SES sca a ce ee ee Bee eee eee es ae ee sie eae 12 Trier nnd owed nie cage ea eee ae Sicag ke aden fonts eas delete cuties See ee eames ace Sale popry tate betel wees pooner fas Maia eas coulis No gal oatentay eat veaintcitaiarndsed ove aamben e, Nore 3—Oils, such as many cuting ol, rustproofing ols, and similar compounded ils, or excessively dark-colored els, that cannot be ana- "his tat method ie ander the jurniction of ASTM Commitee BO2 on evo Prods, Lig Pel nd Lint ane the et responsi of Subeomminee D02.05 on Analysis of Lguld Poss and Laban, Tw the I, this ts method is ander the juriiton of the Standardzon Commie. This test method Was adepted asa ot ASTMEIPsandad ia 196. ‘Creat edkion appoved Dee. 1, 2014, Published Janoay 2015. Ocaly approved in 1948, Last previous eden approved in 2012 a8 D4 12 DOL tousaupos74-14E02, * Sutements deinig tis est metho, ts odicaon and its sigaicnce when opted ola nulig oi of mate wl be ound in Gide DIL? lyzed for acid mumber by this test method due to obscurity of the color indicator end pont, can be analyzed by Test Method DA, The acid rumbers obtained by this colorindleator wst method need. not be rumerially the sume’ as thse obtained by Test Method D6G4, the base rumbers obiained by this color indicator test_metbod need not be ‘numerically the same a5 those obtained by Test Method D4739, but they ae generally ofthe same order of magnitude. 1.3 The values stated in SI units are to be regarded as, standard, No other units of measurement are included in this standard, 14 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 af this standard to establish appro- priate safety and health practices and determine the applica- bility of regulatory limitations prior to use. 2, Referenced Documents 2.1 ASTM Standards:? DII7 Guide for Sampling, Test Methods, and Specifications {or Electrical Insulating Oils of Petroleum Origin D664 Test Method for Acid Number of Petroleum Products by Potentiometric Titration 11193 Specification for Reagent Water 1D4175 Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants 14739 Test Method for Base Number Determination by Potentiometric Hydrochloric Acid Titration 3. Terminology 3.1 Definitions: 3.L.1 acid number, n—the quantity of a specified base, expressed in milligrams of potassium hydroxide per gram of sample, required to titrate a sample in a specified solvent to a specified endpoint using a specified detection system. >For referenced ASTM sands, vit the ASTM webie, wasn, ‘onset ASTM Customer Serie at ercetast rg. Foe dual Book of AST ‘Standards volume infomation, fro he tna’ Docent Summary pgs on tte ASTI website, A Summary of Changes section appears at the end of this standardiy v974 - 14° 3.L.L.L Discussion—In this test method, the indieator is p-napitholbenzein titrated to a green/green-brown end point in 8 toluene-water-isopropanol solvent, 3.12 base suber, nthe quantity of a specified acid, ‘expressed in terms of the equivalent number of milligeams of potassium hydroxide per gram of sample, required to titrate a sample in a specified solvent to a specified endpoint using a specified detection system. 3.1.2.1 Diseussion—In this test method, the indicator is p-naphtholbenzein titrated to an orange end point in a toluene ‘water-isopropanol solvent. 3.13 used oil, n—any oil that has been in a piece of ‘equipment (for example, an engine, gearbox, transformer, or turbine) whether operated or not pai7s 3.2 Definitions of Terms Specific to This Standard 3.211 strong acid number, n—the quantity of base, expressed in milligrams of potassium hydroxide per gram of sample, that is required to titrate @ hot water extract of the sample to a golden-brown end point using methyl orange solution 4, Summary of Test Method 4.1 To determine the acid or base number, the sample is dissolved in @ mixture of toluene and isopropyl alcohol containing a small amount of water, and the resulting single- phase solution is titrated at room temperature with standard alcoholic base or alcoholic acid solution, respectively, to the fend point indicated by the color change of the added ‘p-naphtholbenzein solution (orange in acid and green-brown in, base). To determine the strong acid number, a separate portion of the sample is extracted with hot water and the aqueous extract is titrated with potassium hydroxide solution, using methyl orange as an indicator. 5, Signiffeance and Use 5.1 Now and used petroleum products can contain basic or acidic constituents that are present as additives or as degrada- tion products formed during service, such as oxidation prod- ucts. The relative amount of these materials can be determined by titrating with acids or bases. This number, whether ex- pressed as acid number or base number, is a measure of this amount of acidic or basic substances, respectively, in the cil—always under the conditions of the test. This number is used as a guide in the quality control of lubricating oil Formulations. It is also sometimes used as a measure of lubricant degradation in service; however, any condemning limits must be empirically established, 5.2 Since a variety of oxidation products contribute to the ‘acid number and the organic acids vary widely in corrosive ‘properties, the test cannot be used to predict corrosiveness of ‘an oll under service conditions, No general conelation is, known between acid number and the corrosive tendency of oils toward metals. Compounded engine oils can and usually do hhave both acid and base numbers in this test method. 6. Apparatus 6.1 Burets (withthe following dimensions): ‘Som burt graduates nt subdslons 50m biel grades fr 005 mi or smal lone ‘Sr th 08 mt sbdsine ‘Nore 4—An automated buet capable of deivering tant mount in (0.05 mor smaller increments can be usd bat the stated precision data were obiained using anal bres ony 7. Reagents 7.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests, Unless otherwise indicated, itis intended that all reagents shall conform tothe specifications of the Commit- tee on Analytical Reagents of the American Chemical Society, ‘where such specifications are available.* Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination. 7.2 Purity of Water—References to water shall be under- stood fo mean reagent water that meets the requirements of either Type I, Il, or Il of Specification D193, 73 Isopropyl Alcohol, anhydrous (less than 0.9 % wate). (Warning —Flammable.) 74 Hydrochloric Acid Solution, Standard Alcoholic— (0.1 M)—Mix 9 mL of concentrated hydrochloric acid (Warning—Corrosive, fumes cause initation) (ICI, sp gt 1.19) with 1000 mL.'of anhydrous isopropyl alcohol (2- propanol) (Warning—-See 7.3). Standardize frequently enough to detect molarity changes of 0.0005 (Note 6), preferably by electrometrc titration of approximately 8 mi. (accurately mea- sured) of the 0.1 M alcoholic KOH solution diluted with 125 mL of carbon dioxide-free water. When an electromettic titration is used for the standardization, the end point shall be well-defined inflection point closest tothe cell voltage for the acidic buffer solution, When a colorimetric titration is used for the standardization, titrate to the first stable appearance of the ‘orange color with methy! orange indicator. Nort $—Commescilly avaiable reagents may be used in place of the laboratory preparations when they are eertied to be in accordance With 1 ‘Nore 6—To simply calculations, both the standard KOH and HCL solutions can be adjusted so that 1.00 mL s equivalent to 5.00 mg of KOHL Sodium hydroxide (NoOM) and sulfuric acid (H,80,) can be substituted for KOH and HCI, respectively 7.8 Methyl Orange Indicator Solution—Dissolve 0.1 of ‘methyl orange in 100 mL of water. 7.6 p-Naphtholbenzein Indicator** — Solution—The pp-naphiholbenzein shall meet the specifications given in Annex “Reagent Choncala, American Chomcal Society Speciation, American cena Sosiey, Wisin, DC. Fer Suggestions on the tesing of reagents mo Tse by the American Chemist Soc, se Anal Sadar or Caborory ‘Chemie, BDU La, Poole, Doct UK» a he Ute Stas Parsee ‘and Narn Forma US. Pharmacopenl Convention, ne, (USPC), Roki, MD, tm 2006 soy oly Koda, Baker (Maiko) Fok, and Aléich were ‘oad © meet he seictns in Anaex Al, However, Kodak brandis 0 fopet sale,Ay o974 - 14° AL, Prepare a solution of p -naphtholbenzein in titration solvent equal (0 10 g/L + 0.01 g/L. 7.7 Potassium Hydroxide Solution, Standard Alcoholic (0.1 M)—Add 6 g of solid KOH (Warning—Highly corrosive 1 all body tissue) to approximately I L of anhydrous isopropyl alcohol (containing less than 0.9 % water) in a 2 L Erlenmeyer flask. Boil the mixture gently for 10 min to 15 min, stirring 10 prevent the solids from forming a cake on the bottom. Add at least 2g of barium hydroxide (Ba(OH),) (Warning— Poisonous if ingested, strongly alkaline, causes severe initation producing dermatitis) and again boil gently for Smin to 10 min, Coo! to room temperature, allow to stand for several hours, and filter che supernatant liquid through a fine sintered- ‘glass or porcelain filtering funnel; avoid unnecessary exposure to catbon dioxide (CO;) during filtration, Store the solution in, 1 chemically resistant dispensing bottle out of contact with ‘cork, rubber, or saponifiable stopcock lubricant and protected by a guard tube containing soda lime ot soda nonfibrous silicate absorbent (Ascarite, Catbosorb, or Indecarb). 71 Standardization of Potassium Hydroxide Solution— Standardize frequently enough to detect changes of 0.0005 M. (One way to do this is as follows: Weigh, to the nearest 0.1 mg approximately 0.2 g of potassium acid phthalate, which has been dried for at least Ih at 110°C + 1 °C and dissolve in 40m + ImL of water, free of COs. Titrate with the potassium hydroxide alcoholic solution to either of the follow- ing end points: (7) When the titration is electrometric, titrate 10 «a well-defined inflection point at the voltage that corresponds to the voltage of the basic buffer solution, or (2) When ti is colorimetric, add six drops of phenolphthali solution and titrate to the appearance of permanent pink color. Perform the blank titration on the water used to dissolve the potassium acid phthalate, Calculate the molarity using the following equation: ¥, Molaiy = sis x a where: W, ‘weight of the potassium acid phthalate, g, 264.23 = molecular weight of the potassium acid phthalate, v volume of titrant used to titrate the salt to the specific end point, mL, and ¥, = volume of titrant used to titrate the blank, mb. 1.12 Phenolphthalein Indicator Soluion—Dissolve 0.10 of solid pure phenolphtbalein in 50 mL. of water and $0 mL. of ethyl alcohol Now 7—Commercially available reagents may be used in place ofthe Iaboratory preparations. Nore 8 Because ofthe elatively large cosfcien of cubic expansion of onganie liquids, such as isopropyl alcohol, the standard alcoholic “lations shoul be standardized a temperatures clos to those employed in the tations of samples, 7.8 Tiration Solvent—Prepare by mixing toluene, water, ‘and anhydrous isopropyl alcohol in the ratio 100:1:99. * Sopporing dts have sn Hed at ASTM Iterations Headguarer and may be obiatned by requesting Research Report RR DOD 166 “TABLE 1 Size of Sample "hea Namba or Sie of ‘Svatny af Bae Nonber i Tew origi Ge Wear Oza a5 ‘Ore 28010 2800 2.000 fan, Tensor Cas Wes 20202 30 ‘Over 2562800 a2 +002 oo ‘Up otred eanpie of low 9a numer parle os of 209 sarpes fo ‘bin more pei res, The samp st for dkored of i the ‘quan spel te minniz poste staarene by De dak cao. 8. Preparation of Used Oil Samples 8.1 Strict observance of the sampling procedure described in 8.2 is necessary, since the sediment itself is acidic ot basie ‘or has adsorbed acidic or basic material from the sample. Frilure to obtain a representative sample causes serious errors, 8.2 Heat the sample (Note 9) of used oil to 60°C * 5 °C in the original container and agitate until all sediment is homo- geneously suspended in the oil (Note 10). If the original Container is of opaque material, or if it is more than three- fourths full, transfer the entire sample to a clear glass botle having a capacity at least one third preater than the volume of the sample, and transfer all traces of sediment from the original, container to the bottle by violent agitation of portions of the ‘sample in the original container. After complete suspension of all sediment, strain the sample or a convenient aliquot through 2 100-mesh screen for the removal of large contaminating particles (Note 9) Now 9 When samples are visibly fee of sediment, the heating prcesdre described in 8.2 may be omited, When samples ae visibly free ‘of semen, the sing procedure may also be omit [Nore 10—As used oil can change appreciably in slorage, samples should be tested 4s soon a8 possible afer removal feom the lubcaing system andthe dates of sampling end testing should be noted. 9. Procedure for Acid Number 9.1 Into an appropriate size Erlenmeyer flask or a beaker, introduce a weighed quantity ofthe sample as given in Table 1. ‘Add 100 mL of the titration solvent and 0.5 mL ofthe indicator solution, and without stoppering, swirl until the sample is, entirely dissolved by the solvent. If the mixture assumes a yellow-orange color, proceed as directed in 9.2; if it becomes inreen of green-black, and base number analysis is required, proceed as directed in Section 10. Nore 11a routine analysis the indicator may be pre-mixed with the tration solvent before adding to the sample, 9.2 Without delay, titrate at a temperature below 30°C (Note 14), Add 0.1 M KOH solution in increments and mix t0 disperse the KOH as nevessary (see Note 12). Shake vi ously near the end point, but avoid dissolving carbon dioxide (CO,) in the solvent. (In the case of acidic oils, the orange color changes to a green or green-brown as the end point is approached.) When the solution first turns green or green- brown, reduce the increment size to dropwise (manual bured) or between 0.01 mL and 0.05 mL (automated buret). Continue until @ persistent green or green-brown end point is reached.