AOCS*& AOCS Official Method Ea 6-94 Reapproved 2009, Determination of Crude Glycerin, Titrimetric Method DEFINITION This method determines the glycerol content of industrial glycerins. Glyceral is oxidized by sodium peri ‘odie in a strongly acidic medium. he formic acid produced by the reaction is titrated with a standard solution of sodium hydroxide. ‘The glycerol concent is expressed as a percentage (m/m). SCOPE ‘Applicable co industrial glycerins. This method is nor applicable in the presence of organic compounds containing more than two hydroxyl groups on adjacent carbon atoms, stich as sugars. ‘These compounds may also give rise to formic acid and will interfere in the glycerol determination. Replaces ka 6-51. APPARATUS 1. Conical fasks—500 ml 2. Beakers—rall form, 600 mL. 3. Buret—50 ml, with the jet drawn outso as co allow delivery of 30 drops per ml. and cali of Testing specification. 4, Volumetic asks 500 ml. and 1000 ml 5. Pipec—30 ml. graduated. 6. pH meter—firted with a glass electrode (Notes, 1) 7. Stitrer—preference should be given co a magnetic stirer. In this case, check that it does not influence the pH meter. rated co meet National Insticute REAGENTS I. Distilled warer—or water of equivalent purity, free from carbon dioxide. 2. Ethylene glycol (1 ,2-ethanediol, free from glycerol) —solution in distilled water (Reagents, 1) 1:1 (v/v). 3. Sulfuric acid —aqueous solution, approximately 0.05 M. 4, Sodium hydroxide—aqueous solution, approximately 0.05 M. 5. Sodium mecaperiodate—neutral, iter at least 98% (m/m), aqueous acid solution 60 g/L. (Notes, 2) 6. Sodium formare—aqueous solution, approximately 1 M. Sodium hydroxide—0.1 M aqueous solution, accurately standardized. 8, Sodium hydroxide—0.125 M aqueous solution, accurately standardized, free from carbon dioxide (Notes, 3). 9. Porascium hydrogen phthalate C,H (COOK)(COOH)—0.05 M aqueous solution (10.12 g/t), pH 4.00 at 20°C: (Notes, 4) 10. Disodium cetraborare decahydrate (Na,B,O, « 10H,O)—0.01 M aqueous solution (3.81 g/L, pH 9.22 ar 20°C) (Notes, 4). 11. Phenolphthalein—5 g/L solurion in 95% (v/v) ethanol, 12. Phenol red. PROCEDURE ‘Note—As the presence of cathon dioxide can introduce errors, itis advisable to cover the vessels containing the test solutions with a clock glass during the standing periods and also to avoid enriching the carbon dioxide content of the laboratory atmosphere by other operations carried out at the same time. In the case of alkaline laboratory samples or laborarory samples giving a tarry precipitate on acidification, the procedure indicated under the particular case is to be used. 2. Ifthe approximate glycerol content is not known, it should be determined by a preliminary test on 0.50 g of the laboracory sample. 4: ce preter e 7596 Wel, fle care 0001 95030-0150 giof i lieve, Tanner quanto coe beaker (Apparatus, 2) for determination. 4, Ifthe glycerin content is > 75%: Weigh, to the nearest 0.0001 g, 54 0.1 g of the test sample. Transfer quantitatively to a volumertic lask (Apparatus, 4). Diluce 0 500 ml. with distilled warer (Reagents, |) and mix. ‘Transfer by pipet, 50 mL. of this solution to a beaker (Apparatus, 2) for determination. 5, Particular case: ‘Transfer the rest porrion prepared ac indicated if the glycerol content is not known, 0 an appropriare vessel. Dilute to 50 mL. if necessary. In che presence of 2 drops of the phenolphthalein solution (Reagents, 11), neutralize juse co decoloration by means of the sulfuric acid solution (Reagents, 3). Add 2 5 ml. excess of the sulfuric acid solution (Reagents, 3). Fira reflux condenser. Bring to a boil and maintain boiling for 5 min, Allow to cool. If necessary, filrer Page 1 of 2SAWPING ANDANASR GF CRUDE GIVER Ea 6-94 » Determination of Crude Glycerin, Titrimetic Method and wach wich dslled water (Reagent, 1). Quant deteminaron. lane Tets Cary out, ar che ame tae at che determination and under che sme condone, blak test without he tse rion sng the ame quant of reagents and dating water a for the devermiation, 7. Dereeminaton: Dilute thers sample inthe beaker (Apparat, 2) with dled water Reagent, 1) oa volume of about 250 mL. Ieee the gle electrode and sat ring with these (Apparatus, 7). Neutralize by anean of the sodium Iydonde slution (Reagent, 4) eo pl 79 0.1 checked bythe pH meter (Apparatus 6), With piper (Apparatus, 3) 2d Spenco he run cpeinee slsdeeeagens 3) Ur aheablese peaion Comms ec igh LIke gos and slow co stand foc 30a in the dak a temperate not excending 35° 8. Add 10 ml of the ethylene glcal elution (Reagents, 2). Mix. Allow co stind for 20 ona a the dasa a empeciaze noe cxceoding 35°C 9. Ad 5.00 ml. ofthe sodium Formate soltion (Reagents, 6) with s graduated piper (Apparatus, 5). With the bust (Appar, 3, sate the aide proses with she odin hydroxide solution (Resgens 8) 03 pH 79 20.2, check with the pl sor (Apparat, 6) ively ceansfor the solution obsained to « beaker (Apparatus, ) for Z CALCULATIONS 1. The glyeetal content, expresed a a peccneage (am), ie given by the formu: (W.-M). T. oosar. 1? Where \V, = number of il of the sodium hydroxide solution (Reagents, 8) used for the detemination LV) = number of mL of the sodium hydroxide solution (Reagents, §) used forthe blank tse 1° exact molaiy of the sadium hydioxide solution (Reagents, 8) used ‘me = mass, ing, of gheeria subjected to the reaction with the sodium metaperiodate solution (Reagents, 5) Nores 1, The pl meter should be checked by means of two hulfer solutions (Reagents, 9 and 10). 2. Vesiiation of the sodium metaperiodate neutrality: In a conical ask (Apparaus, 1), disolve 5 g of sodium mecaperiodace in 150 mL of distilled water (Reagents, 1). Add 5 mLofetbylene glycol (Reagents, 2) Allow co stand in the dark and prow ted from atmospheric carbon: dioxide for 30 min. Under these conditions, it should be possible ro neutralize the solution in the presence of phenol red (Reagents, 12) wieh a sodium hydroxide (Reagents, 7) volume of les dhan | mL and preferably less than 0.2 ml Prepare the acidic solution by weighing, o the nearest 0.1 g, 60 g of sodium metaperiodate (Reagents, 5). Dissolve, the cold sodium metapesiodate, with 120 mL sulfusie acid (Reagents, 3), diluted in 500 ml. of water (Reagents, 1). Transfer ro a volumetric flask (Apparatus, 4), dilute to 1000 mL. with wacer (eagents, 1) and mis. IF necessary, filer dhrouy sintered glass Blker ‘Verify the solution acidity —‘The volume of sodium hydroxide (Reagents, 8) used during dhe blank wst (Procedures, 6) should be nor les than 4.5 mL, corresponding to the acidity required for reaction, Stove the solution ia a dark glass lak fied with « ground giss spp. 29. Standard acid —unail a primary standard acd can be esablished internationally, iv is recommended to inerested partes that the standardization ofthe solution (Reagents, 8) be carsied out by means of the same batch of primary standard, 4. Use saundard materials especially prepared for pH] measurements. 5. AOCS Method Ea 6-51 was replaced in the interest of methods harmonization. “This meshod is identical wo IUPAC 3.121, which isso the same as ISO 2879-1975. In addition, the APAG uses ISO 2879-1975. TUPAC = International Union of Pure and Applied Chemisty 150 = Internacional Organization for Standasdization APAG = Aswocation Européenne des Producteurs d’Acides Gras Page 22