Designation: D 974-08 TP. _ Designation: 139/98 Standard Test Method for Acid and Base Number by Color-Indicator Titration’ “his snd i tuner he ed dsipntion DST te nambrmetsy fowig Ms aiznion ines he yeu of ‘sol pion in ca fri he yea ido. A nama rennet eu Wt een ‘Spur pon) nznes one eae se he hs sono apo "seat er brn poe fr ee ances of te Drama of Dees 1. Seopet 1.1 This test method covers the determination of acidic or basic constituents (Note 1) in petroleum products? and lube teats soluble or nearly soluble in mixtures of toluene and isopropyl alcohol. I is applicable fr the determination of acids ‘or 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. Salis react if their hydrolysis constants are larger than 10°” [Nore 1—In new and used oils he consents conridered 10 have sid charceritice ich ngic and inorganic acs esr, phobic ‘Sompound, lactones, resin al of heavy mera, and 0508 gente ach nbior: and detergent Simin, coasts eosideed > have basieproperiesinhad organic and iorzanic bases. amino com ‘pounds, sate of weak ache (ape, bi als of polyalde bases. sas ‘Ot heany metal, and adiion agents Suc as inbliors ané deren Nove 2-This test method i not sable for mensun conativents of many basic sivesype hub D473) canbe used fortis purpose, 1.2 This est method ean be used wo indicate relative changes shat occur in an oil ducing use under oxidizing conditions. Although the svrtion is made under definite equilibrium ‘conditions, the method does not measure an absolute acidic or basie property that can be used to predict performance of an oi under service conditions. No. general relationship between ‘bearing corrosion and acid or base numbers is known Nore 3—Oil, such as many eating ot soon ls and siar compounded ois, oF excessively dasecoored ols that cannot be 23+ Tyzed for acid number by this test muod due to obsewity of the ‘lorndistor end point ca be analyd by Test Method D 64. The acid Ti et eth we he jacion of ASTM Commie D2 09 ie can ta i pny Sibecme ‘Dan0s on Ans Laas ine Ih wat eco yale be pit ofthe Sein ‘Commie This tot mat! wan alped aio ASTRGIP sl a 18. “Cureton ape Joy 20K Panton Aus 2008. Oral speed 918 Lint pevions en proved 207 ve DST07 ‘Shae dy tet tia. lene 2a 5 ight es split cls igi lola wil Be Toad ui 117 ne unbers obuined by this colorindicator test method nee not be ‘numerically the wane a those obtained by Test Mth fn, the Base fumbers obisined by she color india test method weed ot be ‘umescally the sre 4 hove oblate by Test Method D 73 but they fare geverly of he save oer of magaiuds. 1.3 The values stated in ST units are to be regarded as standard, No other units of measurement are ineluded in this standard 14 This standard does not purport 0 address all of te safety concerns, if any, associated with its use. It is the responsibilty of the user of tis standard to establish appro: priate safety and health practices and determine the applica bility of regulary limitations prior to use 2, Referenced Documents 2.1 ASTI Standards: 1D 117 Guide for Sampling, Test Methods, and Speciiea- ‘Mons tor Electrical insulating Cals oF Fesfoeum Origin 1D 64 “Test Method for Acid Number of Petroleum Products bby Potentiometric Titration {193 Specification for Reagent Water D.A175 Terminology Relating to Petroleum, Petrolewn Products, and Lubricants D479 Test Method for Base Number Determination by Porentiometric Hydrachlorie Acid Titration 3. Terminology 3. Definitions: 3.1.4 acid number, a—ihe quantity of base, expressed in rlligrams of povassium hydroxide per gram of sample that is required to titrate a sample to a specified ead point, 3.111 Diseussion—In this test method, the indicator is _p-napliholbenzein trated 1 a green/green-brown end point in 4 woluene-water-isopropanol solvent. “Far fos ASTM sa vis the AST wb wun. oma AST Cre Sere a een Fa ta 9 STL ‘Sends ow tri, tr a= Bom Saray pg “A Summary of Change setion appenes a the end of this sana,ily v 974-08 3.12 base number, n—the quantity of acid, expressed in milligeams of potassium hydroxide per gram of sample tat is fequited to trate @ stinple 10 a specified end point. Siz Discwssiop-cin this est method, the indietor is pnaphiholbenzein titted Yo an orange end point i a toluene ‘water isopropanol solvent. “13 used oil, any oll that has bean in a piece of ceguipment (Cor example, an engine, gearbox, transformes, oF furbine) whether operated or not. baits 3.2 Definitions of Terms Specific to This Standard: 321 strong eid number, a—he quantity of base, ex pressed in milligrams of potassium hydroxide per gram of ample, that is required to Gute a hot water extract of the Sample {0 ® golden-brovn end point using methyl orange solution 4, Summary of Test Method 44.1 To determine the acid or base number, the sample is Gissolved ina mixture of roluene and isopropyl alcohol ‘containing a small amount of wate, and the resulting single- pase solution is tiated at room temperature with standard Flcohotic base or alecholie acid solution, respectively, the fend point indicated by the color change of the added jp naphaholbenzein solution (orange in acid and green-brovn in base). To determine the stfong acid number, a separate portion fof the sample is extracted with hot water and the aqueous fxtract is rated with potassium hydroxide solution, using methyl orange as an indicator 5. Signifieance and Use 5.1 Slow and oped potenti products ean contain basie oF acidic constituents that are present as additives or as dearada tion products formed during service, such as oxidation prod tos. The relative amount of these materials ean be devermined by titrating with acids or bases. This numbes, whether ex: pressed as acid number oF base number, is a measure of this mount of acidic or basic substances, respectively, in the Dilalways under thé conditions of the test, This mamber is fused as a guide inthe quality control of lubricating oil formulations. It is also sometimes used as a measure of Tubrieant degradetio® in service; however, any condemning Jimits must be enipifeally establishes. 32 Since a variefy of Saidation products contribute t0 the acid numer and the orgs acids vary widely in corrosive properties, the test cannot bé used 10 predict cosrosiveness of fin oil ander sérvice conditions. No general correlation is Knowa betweenracid number and the corosive tendency of oils Toward metals. Compounded engine oils can and usvally do have both acid and base numbers in this test method. 6 Apparatus 6.1 Bure (with the following dimensions ‘smb gaeute ink tens ‘Dink ure asiened 90S or sma wiser Swi Oz sbowsors Nose 4—An automate burt capable of devring sant amounts ‘odsmit oe smaller nsenonts ct be used bu he stated precision deta ‘were abisned sing manual butts oy. 7, Reagents 71 Purity of Reagents—-Reaget grade chemicals shall 6& sed inal tess, Unless otherwise indicated, iis ntended that lll weagents shail conform to the specifications ofthe Commit tee on Analytical Reagents of the American Chemical Society ‘Shere such specifications are available* Other grades may be ised, provided it is rst ascertained chat the reagent of afficienity high pority to permit its use without lessening the accuracy of the determination F2 Parity af Water-—ReFerenees to water shall be under. stood yo mean reagent water that meets the requirements of cither Type I Il, oF Ill of Specification D 1193 "73 Iropropy Alcolol, anhydrous (less than 0.9 % wate) (Warning—Flammable) 7.4 Hydrochloric Acid Solution, Standard Alcoholic —(0.1 M}_-Mix 9 mi of concentrated hydrochloric acid (Warning Corrosive, fumes cause ieitation) (HCl, sp gr 819) with 1000 fn of anbydrous isopropy! alcobol (2-propanol) (Warning — Boe 7.3). Standardize frequently enough to detect molarity changes of 0.0005 (Note 6), preferably by electromesric titration of approximately 8 ml- (accurately measured) of the {0.1 M leoholic KOH solution diluted with 125 ml. of carbon tioxie-free water. When an electrometric titration is used (or the standardization, the ead point shall be a well-defined Jnifeetion point closest to the cell voltage for the acidic buffer Solution, When a colorimetric ization is used forthe standaré- jnanion, irate to the first stable appearance of the orange color with aethyl orange indicator Non: 5—Coninercaly avaiable reagents nay be wed in pce of he ameatoy pepratian eon thy ne et be corde one 6 sili cleans, bo the standard KOH and HCH sofa can bs ssed 0 tht 100 tL is eau to 3.0) mg ot ROH Sodan bydeoside (MMOH) and sulfur acid (H,SO,) can Be [nats for KOH and BCL especively 75 Methyl Orange Indicator Soturion—Dissolve 0.1 8 of ethyl orange in 100 mL of water 7.6 p-Nuphiholvenzein Indivator®* Solution The _pnapbtholbenzin shall meet the specifications given in Annex (AI: Prepave solution of p-naphubelbencein in tiation solvent equal 1 10 £001 pi. 77. Potassium Hydroxide Solution, Standard Alcoholic (0.1 M)_Add 6 gof solid KOH (Warning —Highly corrosive to all tbody tissue) to approximately 1 L of anhydrous alcohol (containing Tess than 0.9 water) in a 2-L Erle flask Boil the misture gently for 10 to 15 min, stirring to prevent the solids from forming a cake on the botiom, Ad@ at Menst 2g. of barium hydroxide (BaOH)) (Warning— Tepe Cheats Americ Chea Sis Spc Ames con Sven Masten BC, For Sezai om ees oem Gee Renan Choice Sosy occa Sudo (sna Trea tats Be: Danes UX ame te Che Se Pree cet Pande US. Pamaopeid Coan. USPC, Rach mo, 22006 say. ony Kak ker (Malnhe Faka and Ach wee om na cons Asa X- Howes Kod ba mo es ole, tering he nS AST nnd ean: ly 0974-03 Poisonous if ngesé strongly alkaline, causes severe }itaion ducing dermatitis} and-agan boil gently for 5 to 10 min ‘Cool to room temperature, allow to stand for several hours, and. Alter the supenaiant Tiga through a fine sintered-tass oF porcelain Gerig Tnnel, avoid. unnecessary exposure 10 axibondioride (CO) during filtration Store the solution in a chemically esistan dispensing bottle out of contact with cork rubber, of saponifiable topeack lubricant and protected by & ard tube containing soda lime or soda nontbvous silicate absorbent (Ascarite, Crbosorb, or Indecsb) 741 Standardization of Potassium Hydroxide Sotution— Siandaedize frequently enough to detect changes of 0.0005 N. (One way todo this i as follows: Weigh, tothe nearest 0.1 mg, approximately 0.2 g of potassium acid phihalate, which has been dried for atleast 1h at 110 + 14C and dissolve in 40 Tomb of water, free of COs, Titre with the potassium hydroxide alcoholic solution to either of the following end points: (2) When the titration is electromettic, tate to a well-defined infletion point atthe voltage that corresponds 19 | the voltage ofthe basi buffer solution, or (2) When titration is add six drops of phenolphinalein indicator solu- Xe t0 the appearance of @ permanent pink colo. Perform the blank titration on the water used to dissolve the powssium acid phthalate, Caleulae the normality using the fotowing equation: Wy 1000) Nomatiy = spn Pe o weight of the potassium acid phthalate, g, ‘molecular weight ofthe potassium acid phthalate, ‘volume of titrant used 0 tate the salt to the specie end porat, mL, ana V, = volume of titrant used to titrate the blank, re 4.1.2 Prepare 10.1 = 0.01 mt solution of phenolphthalein by dissolving pure solid phenolphihatein in a 1:1 mixture of ‘water, fee of CO, aud ethanol. ors 1—Cormerily rie agen my eed inp te tery pean Nove Bete th aly ge coe fai expan af eget eo propyl he sand ache ‘Santer sh sence pases cease inte aon of staple 18 Tiron Solient—Piepare by mixing tluene, wir, 3 anyérts oprpyt alec nthe ro 100: 199 8. Preparation af Used Oil Samples 8.1 Stit observance ofthe sampling procedure deserved in 62 is necesny since the sediment isl is acti or baie or has adsorbed soiie of bise material from the sample. Failure to obsin a representative sample cases serio evors. 8.2 Heat the simple oie 9) of use oil 1060 = 8°C in the original container and agitate until all sediment if homoge- ‘ously suspended inthe ol (Nore 10) I the ogi Sonainer is of opaque mate ors i more than three-fourths fll transfer the envite sample fo a clear glss hoe having apacty et east one third. grater than the volume of the sample, snd testy all trices of seciment from the original container othe bate by violent ataton of potions of the TABLE 1 Size of Sample! Tad Naor Brea “easinay a ase Numer sampn.g __Wesheg 2 Tera Wea 20220 oa Oea50 10280 20202 Ed Ser 25016 2500 53 = 002 Boor Tae Oa Tes Oe Wwe 20°02 Tar ‘Over 2516 2500 02 = 002 en: 7 gh canes samples ow asd manta pam wa ol asamp o ‘utsnmore pisces aus The eavpn sooo cnc alse bra othe ‘uinty speotod minnie posse rerence bye ert clr sample in the original container. After complete suspension of all sediment, strain the sample oF a convenient aliqust through 44 100-mesh’ screen for the removal of large contaminating Panicles (Note 9), None 9--Wken samples are visibly free of sediment, the eating procedutedescrted it 2 may be omied. When samples ae visibly Df sient, the esining predce may ao be emt Dore 10—As used oil can change oppreibly in ste, samples shold be test ss s00n a8 posible flr removal rom the lubctng system andthe dates of sampling an esting should Be nt, 9. Procedure for Acid Nomber 5.1 Ino an appropriate size Erlenmeyer Mask or a beaks introduce a weighed quantity of the sarple as given ia Table ‘Add 100 mL-of the titration solvent and 0.5 ml-o the indicator solution, and without stoppering, swirl until the sample is tentiely dissolved by the solvent, If the mixture assures a yellow-orange color, proceed as directed in 9.2 iF it becomes Teen or green-black, proceed as directed in Section 10, Nim, 11—In oun aay th actor may Be pre-med with dhe tivation solve before adn to he sane 9.2. Without delay, irate ata temperature below 30°C (Sie 14), Add 0.1 M KOH solution in increments and mix 10 disperse the KOH as necessary (ee Note 12). Shake vigor- ‘ously near the end point, but avoid dissolving carbon dioxide (CO) in the solvent, (In the case of acidic ols, the orange ‘color changes 10 8 green or green-brown as the end point is approached.) When the solution first urns green or green ‘brown, reduce the increment size to dropwise (manual buret) or ‘pesween 0.01 and 0.05 mL (automated buret). Continue until persistent green or green-brown end point is reached (see Nove 13) an held fora minimur of 13 s alter the addition of the lst ‘Inorement or if It reverses with two drops of 0.1 Mf HCL [Non 12--Whon ae numbers abot oslo one re expected eter cin ca be obined by sbstuting 0.01 gr 008 solations in) > fd 9.8. This substation wns ot sacladed in he development of precision xaement [Nore 13-To aber the epi of darko i, take the Hak igoroaly vo prodace momontcly a sight foam when Ie clr hangs ‘veut the asf drops of an are added ad serve the tao hoeescon amp at bec top lve Nott 14--The epee ca be inured By any wetable taper we measuring device Nore 1S-An suiomated photomtrie device may ao be sed ode the iain end pil However, te precision estimates given in Seton 1S ay no ply thie roc of ration