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    Aocs Vi - F - S3 64

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    OFFICIAL METHODS AND RECOMMENDED PRACTICES OF THE AOCS Analysis of Sulfonated and Sulfated Oils These methods are applicable to the analysis of surface active agents of the sulfuric acid ester (sulfate) and sulfonic acid (sulfonate) types. In the former, there is an oxygen bridge between sem the sulfur and the carbon atoms whereas in the latter the sulfur is bound directly to the ea bon atom. The sulfuric acid ester or sulfate type is distinguished from the true sulfonate type by the fact that itis hydrolyzed upon boiling with mineral acids to yield free sulfuric acid WARNING Some of the methods contained in this section require the use of flammable, toxic, haz~ ardous and/or poisonous materials. Manufacturers’ safety instructions and the cautionary statements included in the methods for handling these materials should be observed. ‘Methods requiring the use of hazardous and toxic materials should be carried out in a prop- erly operating fume hood, to prevent exposure of laboratory personnel. Appropriate protec- tive clothing and equipment should be used. See the Laboratory Safety section of this book ANALYSIS OF SULFONATED AND SULFATED OILS AOCS& AOCS Official Method F 12-44 Reapproved 2009 Moisture, Distillation Method DEFINITION This method determines the moistute by distilation wich an immiscible solvent. SCOPE ‘This method is applicable o sulfonated and sulfated oils excep those that contain any ofthe following: mineral acids, fee sulfonic acids, free sulfuric acid esters; alkali hydroxides, carbonates, or acetates; alcoho, glycerol, dieshylene glycol, acetone, or other water-miscible volatile compounds ‘APPARATUS 1. Glass distillation apparatus—constructed as shown in Figure 1, with the fll (a) Flask—500 mL, Erlenmeyer or short-neck, round-botiom type. (b)_Condenser—water-cooled, the lower tip of which shall be about 7 mm above che surface of the liquid in the trap after distillation conditions have been established, (2) Trap—conscructed of well-annealed glass and graduaced to contain 5 ml. at 20°C. It shall be subdivided into 0.1 mL. divisions with each 1 mL. line numbered and the 5 mL line at the top. The ertor at any indicated capacity shall not exceed 0.05 mL. (d)_ Distillation is better controlled by wrapping the tube which leads from the flask to the receiver with 100% fiberglass cloth tape. Ie is advantageous to wrap the flask also, especialy if there are drafts in the vicinity of the distllaci apparatus. (6) See Procedure forthe calibration of the distillation apparatus. 2, Pipet—measuring type, capacity 1.0 mL, graduated in 0.01 mL, 3. Heat source—preferably an electric heater provided with a suitable means of contol, 4. Copper or nicirome wite—long enough (0 extend through the condemser with one end cvisted into a spiral. The diameter ofthe spiral should be such that ic will fr sougly within the receiver and yet can be moved up and down. specifications — REAGENTS 1. Xylene—reagent grade (see Notes, Caution). 2. Oleic acid USP grade ot equivalent, Heat for 5~10 min ata temperature not exceeding 130~135°C before using PROCEDURE Note—The entte apparatus mast be entirely clean and completely dry before using Itis recommended that the apparatus be fist ‘washed with soap and warm water, rinsed well and then created wich dichromate/sulfuric acid cleaning solution 1. Calibrate the receiver by the following procedure: Add an accurately measured portion, 1 © 0.01 mL, of distilled water to 100 mL of xylene in the distillation flask. Conduct the distillation as described in Procedure, 3-6, and ealeulate as directed in Calculations. Cool dhe apparatus, add another 10.01 mL. of water and repeat che distillation. Continue in this manner up to the capacity of che receiving tube. 2. Weigh a sulficent quantity of che test sample into the distillation flak to yield about 4 mL. of water. Ths is conveniently done using a weighing bottle. Add 100 mL of xylene and an amount of oleic acid equivalent to about 2.5 times the weight ofthe dry test portion. This is done to prevent the test portion from foaming and forming ajlly-like mass. 3. Introduce some glass beads to prevent bumping and mix the contents ofthe fas thoroughly by swirling, Assemble the ‘apparatus and fill the receiver with solvent by pouring chrough the condenser until che solvent begins to overflow into the distillation flask. Insett a loose cotton plug in the tip of the condenser to prevent condensation of atmospheric moiscure within the tbe 4, Heat the flak so that che distillation rate will be about 100 drops per minute. When the greater part of che water has dis tilled, increase the distillation rate ro about 200 drops per minute and continue uni the water level in the receiver cemains unchanged for 30 min, 5. Discontinue heating, dislodge any drops of water which may be adhering to the inside of either che condenser tube or recciver with the wire spiral, and wash down with 5 mL of xylene 6. Immerse the receiver in water at 40°C for 15 min or unl the xylene layers lear, Read the volume of water and determine the cemperature ofthe water, Refer to Table 1 for the specific gravity (ap. ge) of water a the temperature determined. CALCULATIONS vol wate, mb x Moisture 99 = SSS ESP 9g mas of tt portion Page 1 of2 ‘ANALYSIS OF SULFONATED AND SULIATED OWS F 1a-44 » Moisture, Distillation Method NOTES Casaion ‘Xylene is flammable and a dangerous fie risk, The TLV is 100 ppm in air, Use a fame hood when heating or evaporating. Tables TemperauureC Speaifie Gravity 4 1.000 35 0.994 36 0.994 7 0.993 38 0.993 39 0.993 40 0.992 4 0.992 a2 0.991 - 3 91 44 0991 45 0.990 ss-127mmod. | 4400 mm 40.2 2mm 295-240 mm | cacy St aduntedin0% mt, | e188 mene | Figure 1. Moisture distillation apparatus. age 2 of 2 ANALYSIS OF SULFONATED AND SULEATED O1LS Se LOCS* AOCS Official Method F 1b-44 Reapproved 2009 Moisture and Volatile Matter, Hot Plate Method DEFINITION ‘This method determines the moisture and other substances volatile at about 100°C. SCOPE ‘This method is applicable to sulfonated and sulfated oils that do not contain mineral aids, fee sulfonic acids, or five sulfuric acid esters; ammonia; acetic acid or similar volatile acids; alkali hydroxides, earbon- ates, acetates or similar salts which may react with oleic acid at clevated temperatures, liberating volatile acids; glycerol, diethylene glycol, xylene, or other compounds of similar volatility ‘APPARATUS ‘Weighing borcle—glass-stoppered, 10-15 ml Beaker—Grffin low form, 150 ml, 50 mum dia Electric hot plate—which may be covered with a heat resistant matctal vo spread the heat if desired. ‘Thermometcr—graduated from 90-150°C, about 76 mm long and substantially constructed Desiceator—containing an efficient desiccant. Calcium chloride may not be reliable See AOCS Specification H 9-87 for desiceanes. REAGENTS 1. Oleic acid —USP grade or equivalent. PROCEDURE 1. Weigh about 5 g of oleic acid into the beaker and insert the thermometer. Heat gradually on the hot plate, stering with the thermometer until the temperature reaches 130°C. 2, Place the beaker in an oven at 105-110°C for 15 min, cool in the desiccator to room temperature and weigh. Repeat the heating on the hot plate and in the oven until wo successive weighings differ by less than 1.5 mg. 3. Weigh accurately about 6 g of the test sample into the beaker containing the oleic acid. This is conveniently done from a weighing bottle. Heat the mixture exactly as described in Procedure, 1 and 2, Cool ina desiccator to room emperature and ‘weigh. CALCULATION = el th te ‘mass of test portion Moisture and volatile matter, %6= x 100 Frage 1 of ANALYSIS OF SULFONATED AND SULFATED OILS LOCS* AOCS Official Method F 2a-44 Organically Combined Sulfuric Anhydride, Titration Method DEFINITION This method determines the organically combined sulfuric anhydride. SCOPE Applicable co sulfated oils that split off their combined SO, upon boiling with mincral acids and that do not contain compounds which cannot be accurately titrated in water solution with methyl orange as the indicator. Only that portion of sulfur bound through oxygen to carbon is determined. Sulfur bound directly to carbon, i. true sulfonate, is noe determined. APPARATUS 1. Exlenmeyer flask—300 mL, with air condenser 915 mm long, glass stopper, and Ts 24/40, 2. Glass beads—made of chemically resistant glass, about 4 mm dia and perforated. Before using the beads, boil them thor- oughly in several portions of distilled water until the wash water is neutral to methyl orange. REAGENTS 1. Sodium hydroxide (NaOH), 1.0 M—accurately standardized (see AOCS Specification H 12-52 for standardization procedute). 2. Sulfuric acid (H,S0,)—about 0.5M (see Notes, Cassin). 3. Diethyl ether—feagent grade (see Notes, Caution). 4 Sodium chloride (NaCI) —reagene grade 5. Methyl orange indicator—0.19 in distilled water PROCEDURE 1. Determine the alkalinity as directed in AOCS Oficial Method, F 7-44. 2. Accurately weigh exactly 10 g of the test sample into a 300 mL Erlenmeyer flask. Add suflicient 0.5 M H,SO, ro neuteal- ine exactly the total alkalinity as determined by method F 7-44, plus 25 ml. in excess. Adda fow glass beads. Attach the ait denser and boil for 1.5 hor until che oil and water layers are perfectly clear. Regulate che heating so that che solution boils igorously, buc with very little evaporation. ‘ool the contents of the flask and wash down the condenser with a spray of distilled water from a wash bottle. Disconnect the condenser and add 30 g of NaCl, 25 mL of diethyl ether, 50 ml. of distilled water, and 2 or 3 drops of indicator. ‘Note—The titration should be caried out in a properly operating fume hood. 4. Titrate with 0.5 M NaOH to the same end point asin the alkalinity titration. Stopper the flask and shake thoroughly several times during the titration. Wait 3 min before reading the burette 5. Conduct a blank determination using 25 mL of 0.3 M H,SO, simultancously with the test portion and similar in all 6, Reserve the tiated solution fr che determination of toa deslGed fury mater by AOCS Official Method F 3-44 CALCULATIONS, Organically combined sulfuric anhydride, 9 = (T — B) x 0.8007 Where— ‘T = volume, mL of 1.0 M NaOH required by test postion B = volume, mL of 0.5 M NaOH required by blank NOTES Caution Sulfuric acd isa stong acid and will cause severe bur oxidizing agent and should not be stored in the vicini ‘evolution that can cause explosive spattering. Al Protective clothing should be worn when working with this acid, [eis an of organic materials. Use great caution in mixing with water due to heat ys add the acid to water, never the reverse. Page 1 of 2 [ANALVSS OF SULFONATED AND SULTATED O1lS F'2a-44 © Organically Combined Sulfuric Anhydride, Titration Method Diethyl ether is highly flammable and is a severe fire and explosion hazard when exposed to heat or flame. Iti a central nervous system depressant by inhalation and skin absorption. It will form explosive peroxides upon exposure to light. Handle empty containers, particularly those from which ether has evaporated, with extreme caution. Explosive limits in air are 1.85— 48%. The TLV is 400 ppm in air. A fume hood should be used at all times when using ethyl ether NUMBERED NOTES 1. The factor of 0.8007 is based on the use of N8OH molarity and of the test portion weight as specified in Reagents and Procedure. Any deviation from these specifications will produce ersoncous results Page 2 012 ANALYSIS OF SULFONATED AND SULFATED OILS LOCS AQCS Official Method F 26-44 Respproved 2009, Organically Combined Sulfuric Anhydride, Extraction-Titration Method a Eee DEFINITION This method determines the organically combined sulfuric anhydride. SCOPE Applicable only to sulfated oils that split off their combined SO, upon boiling with mineral acids, includ- ing test samples containing sodium acetate or other compounds thar eannot be accurately titrated in water solution with methyl orange as the indicator. Only that portion of sulfur bound through oxygen to carbon is determined. Sulfur bound direcly o carbon, ie..a true sulfonate, is not determined ‘APPARATUS 1. Enlenmeyer flask—300 mL. with glass stopper. 2, Separatory Funnel—250 mL. REAGENTS 1. Sodium hydroxide (NaOH), 0.5 M—accurately standardized (see AOCS Specification H 12-52 for standardization proce- dure). Also see Notes, 1. 2. Sulfuric acid (H,SO,)—abour 0.5 M (see Notes, Caution), 3. Diethyl ether—reagent grace (See Notes, Caution) 4, Sodium chloride (NaCl)—reagene grade. 5. Methyl orange indicator—0.1% in distilled water. 6. Sodium chloride solution—saturated in distiled water. PROCEDURE 1. Separation of purified oil— {@) Weigh 5-10 gof che test sample, depending upon the concentration ofthe faery mater, into a 250 mL. separatory funnel containing 50 ml. of sarated NaCl solution, afew grams of solid NaCl, 2 or 3 drops of indicator and 50 mL of diethyl ther Note—This operation should be caried out in a properly aperating fume hood. (8) Shake the mixture and neutralize with 0.5 M H,SO, until the lower layer is distinctly pink (about 0.2 mL in exces) ‘At this stage, highly sulfated oils may form dhtce parts diethyl ether and one part 95% alcohol, v/, ether. (©) Allow the mixture inthe separatory funnel to setle for ac least 5 min, draw off che lower layer into another separatory funnel, and continue washing the diethy! ether layer with 25 mL portions of saturated NaCl solution until 1 drop of 0.5 M NaOH tums the wash water strongly alkaline when methyl orange indicator is used (4) Allow all separations to setleat least 5 min, Combine the water layers and extract with two 25 mL portions of diedhyl ether. Combine the last ewo ether extracts and wash with saturated NaCl solution until fice from acid, a in the case of the diethyl ether layer in che funnel (© Combine all the diethylether layers in the 300 ml. Erlenmeyer flask and evaporate on either a steam or a water bath. 2. Determination of increase in acidity upon boiling, designated as *F"— (2) Determine the increase in acidity upon boiling as described in AOCS Official Method, F 2a-i4, Procedure 2-5. (See Notes, 1). (b) Conduct a blank determination simultancously with the test portion and similar in all respects. (©). Reserve the titrated solution for the determination of total desulfated fatty matter by AOCS Official Method, F 3-44 CALCULATIONS Organically combined sulfuric anhydride Where— 0.1426 = 0.1 of the molecular ratio of SO,/KOH F « increase in acidity in mg KOH/g. ‘vo, In such eases, use a fr solvent consisting of owo 041426 x F Page 1 of 2 ANATES OF WILFONATED AND SUUNED OS F 2b-44 * Organically Combined Sulfuric Anhydride, Extraction-Titration Method NOTES Caution Sulfuric acid isa song acid and will cause severe burns. Protective clothing should be worn shen wo! oxidizing agent and should not be stored in the vicinity of organic materials. Use great caution in mi evolution that can cause explosive spattering. Always add the acid to water, never the reverse. Diethyl ether is highly flammable and isa severe fire and explosion hazard when exposed to heat or flame. Ie is a central ner- ‘vous system depressant by inhalation and skin absorption, e will form explosive peroxides upon exposure to light. Handle empey Containers, particularly those from which ether has evaporated, with extreme causion. Explosive limits in air ate 1.85~48%%, The TTLV is 400 ppm in air. A fume hood should be used at all times when using ethyl ether. ing with this acid. Ic isan ig with water due ro heat NUMBERED NOTES 1. Although sodium hydroxide is used in the procedure, results are expresed based on mg KOH/gram. The factor used in the ‘alculation is based on the fact that 1.0 mL of 1.0 M NaOH solution is equivalent ro 56.1 mg of KOH. age 2 of 2 ANALYSIS OF SULFONATED AND SULFATED OILS AOCS& AOCS Official Method F 2c-44 Organically Combined Sulfuric Anhydride, Ash-Gravimetric Method DEFINITION This method determines the organically combined sulfuric anhydride SCOPE Applicable to all types of sulfonated and sulfared oils, including true sulfon sodium acetate or similar partially teraeable compounds. acid oils and those containing APPARATUS, 1, Crucible—50 mL, high form. 2. Beaker or Soxhler flask—150 mL. 3. Beaker—250 mL. 4, Separatory funnel—250 mL. REAGENTS 1. Diethyl ether—reagent grade (see Notes, Caution). 2. Sodium chloride (NaCl)—reagent grade. 3. Sodium sulfate—anhydrous Na,SO,, reagent grade. 4, Methyl orange indicator—0.1% in distilled water. 5. Hydrogen peroxide—30% (see Notes, Caution). 6, Sodium hydroxide (NaOH)—approximacely 1 M for Procedure, 2, PROCEDURE 1. Absence of ammonia— (2) Proceed as described in Separation of Purified Oil, AOCS Oficial Method, F 2b-44, Procedure, 1, combining the diethyl ether layers in the first Funnel rather than in the Erlenmeyer flask. (6) Carefully remove any water that may srt and dehydrate the diethylether layer by adding 5 g of anbydrous Na,SO,, shaking vigorously for 5 min, and filtering directly nto a 150 ml. beaker or ask, placed in bath of warm water. ‘Note—This operation should be caried out ina properly operating fume hood, (©) Wash the flask and fleer with diethyl ether until free from fat (absence of ol stains om the filer paper after drying) and. add the filtrate to the beaker, To prevent the ol from creeping, te volume inthe beaker or flask should at no time dure ing the filtering and washing exceed 50 mL. (4) Evaporace the diethyl ether solution until the volume has been reduced to about 20 ml. and transfer the residue to a tared 50 mL crucible (6) Place the crucible in a heaker containing warm water uncil practically ll of the diethyl echer has evaporated. Rinse the beaker with ewo 10 ml. and three 5 mL. portions of diethylether, oF until all ofthe oil has been transferred to the era cible. Allow cach portion of diethylether to evaporate before adding the nex. (8) Sei che solution with a glass rod to hasten evaporation and to prevent the oil from creeping. Wipe the glass rod with ashless filer paper and add the paper o the crucible before the oils ignited (@) Ignite the solvent-free residue gently and finally ignie a a dull red heat (500~550°C) to constant weight (8) Moisten the ash with 30% hydrogen peroxide and again ignite carefully to constant weight. Cool in a desiccator con: taining an efficient desiccant to room temperature and weigh (see Notes, 1) (See Calculations, 1 2, Presence of ammonia— {@) Dissolve 5-8 g of the test portion in 80 mL of water in 2250 mL beaker. Add 10 mL of 1 M NaOH and boil the solu tion gently until wet litmus paper no longer indicates ammonia. (©) Cool the solution, transfer to a 250 mL. separatory funnel, and add about 25 g of solid NaC. (©) Add 2 or 3 drops of methyl orange indicator and proceed with the neutralization, extraction, and following steps as directed in Procedure, 1, a-h (A) See Calculations, 2, Page 1 of 2 “GRADS OF SULFONATED AND SULFATED ONS 2e-4 © Organically Combined Sulfuric Anhydride, Ash-Gravimetric Method CALCULATIONS offah 1, Extracted Ash, 6 mau x 100 2. Organically combined sulfuric anhydride, % » 1.1267 x 96 extracted ash. Where 1.1267 « the molecular ratio of 2(S0,)/Na,SO, NOTES, Caution ‘Dieehyl ether is highly flammable and is a severe fire and explosion hazard when exposed to heat or flame, It isa central nervous system depressane by inhalation and skin absorption. Ic will form explosive peroxides upon exposure to light. Handle empty Containers, particularly those fiom which ether ha evaporated, with extreme caution. Explosive limits in ai are 1.85489. The ‘TLV is 400 ppm inair. A fume hood should be used a all times when using diethyl ether. Tijdvogen peroxide isa strong oxidizing agent and a dangerous Fire and explosion risk. Concentrated solutions can cause burns and are highly toxic and strongly isitating, The TLY in air is 1 ppm. NUMBERED NOTES 1. The addition of hydrogen peroxide is for the purpose of oxidizing traces of carbon or sodium sulfide chat may form. Page 2 of 2 ANALYSIS OF SULFONATED AND SULFATED OILS LOTS % AOCS Official Method F 3-44 Reapproved 2009 Total Desulfated Fatty Matter DEFINITION This method determines the total desulfared fatty matter in the test sample SCOPE Applicable to sulfaced oils, bur not co test samples that are not completely decomposed upon boiling with ‘mineral acids. ‘APPARATUS 1, Separatory funnels—250 mL. 2. Beaker or Soxhles flask—150 mL. REAGENTS. 1, Sulfurie acid (H,SO,)—approximately 0.5 M. 2. Diethyl ether—teagent grade (see Notes, Caution). 3. Methyl orange indicator—0.1% in distilled water PROCEDURE 1. Use the ritrared solution abtained from the determination of organically combined sulfuric anhydride by AOCS Official Method, F 2a-44 or F 2b-44, of ates solution prepated in a similar manner, 2. Cool and transfer che titrated solution to a 250 ml separatory funnel, add 50 ml. of diethyl ether, and shake, 3. Allow the layers to separate and then draw off che lower water layer into another similar separatory Funnel. Ex solution ewe more times using a 25 ml. portion of diethyl ether each time. 4, Combine che diethyl ether extracts into one funnel and wash with 15 mL portions of distilled water until dhe wash water is neutral ro methyl orange. 5. Transfer the det eer exacts na aed 150 ml eke or fas which hasbeen hed and cole na deseo, 6. Evaporatethe diethyl ether in a water bath under a gentle stream of clean, dry nitrogen. Note—This operation should be caried out in a properly operating fame hood, Make certain that all races of diethyl cher are removed before transferring to the drying oven. 7. Dry im an air oven at 105 & 2°C for 30 min. Cool in a desiccator to room temperature and weigh. Repeat until constant ‘weight is obeained 8. Reserve the extracted fatty matter forthe subsequent determination of unsaponifiable matter by AOCS Official Method, Psd ot the water CALCULATIONS Total desulficed facty matter, o = —Mes ote es of rile _ 5 100 ‘mas of tex portion NOTES Caution Diechyl ether is highly flammable and is a severe fire and explosion hazard when exposed to heat or flame. It isa central nervous system depressant by inhalation and skin absorption. Ic will form explosive peroxides upon exposure co light. Handle empty containers, particularly those from which ether lias evaporated, with extreme caution. Explosive limits in air are 1.85-48% The ‘TLY fs 400 ppm in ait. A fume hood should be used a all times when using diethyl ether. Sulfuric acid isa strong acid and will cause severe burns. Protective lothing should be worn when working with this acid. Ie is a dehydrating agent and should nor be stored in the vicinity of organic materials, Use great caution in mixing with water due to heat evolution that can cause explosive spattering, Abvays add the acid to water, never the reverse Page tof ANALYSIS OF SULFONATED AND SULFATED OILS Q LOCS AOCS Official Method F 4-44 Reappeoved 2009 Total Active Ingredients DEFINITION This method determines the total active ingredients as they exist in the original res sample. SCOPE . " Applicable co sulfonated or sulfated oils. Free alkali or alkali bound as soap isnot included. Unsulfated and uunsulfonated oil and unsaponifizble fatty matter are included, Note—In che case of sulfated oils only, he toral active ingredicnes may be estimated by calculation, because they are equivalent to the sum of the desulfated fatty matter and neutralized organically combined salfaric anhydride see Calculations, 2). | REAGENTS 1. Diethyl echer—reagent grade (see Notes, Caution) 2, Sodium chloride (NaCl) —reagent grade. 3. Sodium sulfate (Na,SO,)—anhydrous, ceagent grade. 4, Methyl orange indieator—0.1% in distilled water. 5. Alcoholic potassium hydroxide (KOH) solution, 0.5 M— accurately standardized (see AOCS Specification H 15-52 and Notes, Caution). PROCEDURE 1. Proceed as directed in AOCS Official Method, F 2c-44, Procedut, 1 retaining the separated active ingredients in the 150 mL beaker instead of transferring to a crucible. In this case, the beaker must be previously dried, cooled in a desiceator to room temperature, and weighed. 2. Evaporate to a volume of about 20 mL and chen add exacdy 2 ml. of alcoholic KOH solution, Mix by swirling and then evaporate until free from diethyl ether (see Notes, Gaution and 1). The diethylether may be evaporated in a water bath under a gentle stream of clean, dry nitrogen. ‘Nowe—This operation should be carried out ina properly operating fume hood. Make certain that all traces of diethyl ther are removed before transferring to the drying oven. 3. Dry in an air oven at 105 4 2°C for 1.5 h. Cool in a desiccator to room temperature and weigh. Repeat drying for 30 min periods unl a constant weight is obrained CALCULATIONS 1. Total active ingredients, = ast ofrsidue — alll conection 9 ‘mass of test portion Where— Alkali correetion (0006791 x (eal. KOH > §) 0.006791 “H)/KOH divided by 1000 S = strength of KOH solution in mag KOH per mL 2, Sulfaced ils only— Total active ingredients (by calculation), % = P+ 1.4871 x¥ Where— lecular ratio of NaSO,7/SO, ‘oral desulfated fatty matter from AOCS Official Method, F 3-44 combined SO, from AOCS Official Method, F 2c-44 ‘The factor 1.4871 is based on the assumption that che desulfated fatty matter becomes polymerized at the point where the SO, splits off and that no hydroxyl groups are formed. IF the later are formed, the factor becomes che molecular ratio of (NaSO, ~ 1/80} = 1.275. Calculated results were in better agreement wichactual determinations when the higher factor was used NOTES Gaution Diethyl ether is highly ammable and isa severe fire and explosion hazard when exposed to heat or lame. It isa central ne vous system depressant by inhalation and skin absogption. Ic wil frm explosive peroxides upon exposure co light, Handle empty Page 1 of2 RAIS OF SULFONATED AND SULFATED OW F 4-44 « Total Active Ingredients containers, particularly those from which ether has evaporated, with extreme caution. Explosive limits in air are 1.85-48%. The TLV is 400 ppm in air. A fume hood should be used at all times when using diethyl ether orassium hydroxide can burn skin, eyes, and respiratory tract severely. Wear heavy rubber gloves and face shield to protect against concentrated alkali liquids. Use an effective fumeremoval device or gas mask to protect respiratory tract against alkali dusts or vapors. When working with extremely caustic materials like sodium hydroxide and potassium hydroxide, always add pellets to ‘water and not the reverse. These alkalis are extremely exothermic when mixed with water. Take precautions to contain the caustic Solution in che event che mixing container breaks from the extreme heat generated. NUMBERED NOTES 1 With highly sulfonated or sulfated oils, it may be necessary to add 5-10 ml. of the alcoholic KOH in order to stabilize the residue. Page 2 of 2 ANALYSIS OF SULFONATED AND SULFATED OILS AOCS& AOCS Official Method F 5-44 Regpproved 2003 Unsaponifiable Nonvolatile Matter DEFINITION This method of analysis determines the unsaponifiable, nonvolatile (above 80°C) matter, SCOPE Applicable to sulfated oil. ‘APPARATUS: 1. Erlenmeyer flask—300 mL, with air condenser 915 mm long, glass stopper, and 24/40. 2. Separatory funnels—250 ml. 3. Beaker or Soxhlet lask—150 ml. REAGENTS 1, Aqueous potassium hydroxide (KOH), 0.5 M—accurately standardized (see Notes, Caution) 2. Alcoholic potassium hydroxide—approximately 0.5 M, buc not less than 0.5 M (sce Notes, Caution). 3. Diethyl ether-—reagent grade (sce Notes, Causion) 4, Hydrochloric acid (HCI) —reagent grade, sp. gr. 1.19 (see Notes, Caution). 5. Phenolphthalein indicator—1.0% in 95% ethyl aleohol. PROCEDURE 1. Use the residue of exacted fay mater obtained from the determination of total desulfaed fatty matter by AOCS Offical Method, F 3-44, or a text sample prepared in the same manner 2. Weigh accurately 2-255 g of the faty matter into the flask and add 25 mL. of the aleoholi ‘condenser and heat at a low temperature for 1. ‘Note—The temperature should be such thatthe test sample is hot, but without boiling and with no loss of aleohol during the 1 hr heating period. Swiel occasionally. 3. Transfer the contents of the flask to a 250 ml. separatory funnel and wash the flak several times with distilled water, using a total oF 50 mL, Pour the water from the flask into the separatory funnel. 4. While the solution is sill warm (about 30°C), add 50 mL. of diethyl ether, Wash the saponification flask with the diethyl «ther before adding it tothe funnel. Shake vigorously for about I min and then allow the layers to separate (see Notes, 2). 5. Draw off the lower layer into another similar separatory Funnel. Extract this solution two more times, using 50cm. portions of diethyl ether each time (see Notes, 3) 6. Combine the diethyl ether extracts into a separatory funnel and add 20 mL of distilled water. Turn the separatory fannel and contents over gly about six times and then allow the layers to separate. Draw off and discard the lower layer. 7, Wash the diethyl ether layer vice more with 20 mL portions of distilled water, shaking vigorously ater cach addition 8. Add 20 mL of aqueous 0.5 M KOH to the diethyl ether and again turn the separatory funnel and contents over gent about six times, Allow the layers to separate, draw off and discard the lower layer. 9. Wash the diediyl ether layer with 20 mL of distilled water followed by 20 mL. of aqueous 0.5 M KOH, as described in Procedure, 7 and 8. Repeae this procedure until the alkaline layer is only faincy opalescent ater it has been made strongly id with HCI (sp. gr. 1.19) and allowed to sctle for a few minutes. 10. Finally, wash the diethyl ether layer with 20 mL portions of distilled water until the wash water is no longer pink to phenolphthalein, 11. Transfer che diechy ethet layer to a tared 150 mL beaker or flask which has been dried and cooled in a desiccator. Evaporate a water bath undera gente stream of clean, dry nitrogen. ‘Note—This operation should be carried out ina properly operating fume hood. Make certain tha all aces of diethyl ‘ether are removed before transfering to the drying oven, 12, Heat the beaker at 75-80°C in an air oven, Cool in a desiccator to room temperature and bring to conseant weight (see Notes, 4) KOH (see Notes, 1). Attach the CALCULATIONS insaponifiable nonvolatile matter, % sms gofresidue x 9 desulfced fitey matter mass, gof deviled fatty matter Page 1 of 2 ANAISIS OF SULFONATED AND SULFATED O15 F 5-44 * Unsaponifiable Nonvolatile Matter NOTES Caution Potassium hydroxide can burn skin, eyes, and respiratory tract severely. Wear heavy rubber gloves and face shield to protect against concentrated alkali liquids. Use an effective fume-removal device or gas mask ro protect respiratory tact against alkali dasts 0; vapo:s. When working with extremely caustic materials like sodium hydroxide and potassium hydroxide, aways add pellets to water and not the reverse. These alkalies are extremely exothermic when mixed with wates, Take precautions 1 contain the caustic solution in the event the mixing container breaks from the extreme heat generaced, Diethyl ether is highly flammable and is a severe fire and explosion hazard when exposed ro heat or flame. Iti a central nervous system depressant by inhalation and skin absorption. Ic will form explosive peroxides upon exposure to light. Handle empty containe's, particularly those from which ether has evaporated, with extreme caution. Explosive limits in air ae 1.85—48% ‘The TLV 's 100 ppm in air, A fame hood should be used a all :imes when using diethylether. Hydiachlovie seid isa strong acid and will cause severe burns. Protective clothing should be won when working with this acid, Iris roxic by ingestion and inhalation and a strong irvitant to eyes and skin. The use of a properly operating fume hood is recomimienced. NUMBERED NOTES 1. A 3096 alcoholic KOH solution by volume is che most satisfactory solution from which to extract the unsaponifiable Ti esmuisions form, add 5 mL of alcohol by pouring ic down the side ofthe funnel {is unportant to maintain the volume of diethylether at not less than 150 mL, otherwise small quantities of unsaponifable snatier may he lost 4. The presence of fatty acids in the unsaponifiable matter is determined by dissolving the residue in 10 mL of freshly boiled neuttal alcohol and titrating with 0.1 M alcoholic KOH solution, using phenolphthalein as the indicator. Not more than 0.1 ol should be requited for neutralization. IF more is required, the determination has not been cartied out effectively and inust be repeaced 2 3 Page 2 of2 ANALYSIS OF SULFONATED AND SULFATED OMS. LOCS% AOCS Official Method F 6-44 Reapproved 2009 Inorganic Salts DEFINITION ‘This method determines the inorganic sulfates, chlorides and all other salts that are insoluble in a mixture of oleic acid and carbon tetrachloride. SCOPE Applicable co sulfonated and sulfated oils. ‘APPARATUS 1. The fileration must be performed with tared, ashless filter paper. Use Whatman no. 40, 9 cm, or equivalent grade of ashless paper 2. Porcelain ignition crucible—tared, 3. Beaker—250 mL. 4, Hot plate—temperature controlled. REAGENTS 1. Oleic acid USP grade, oF equivalent. 2. Carbon tetrachloride (CCI,)—reagent grade (ee Notes, Caution and 2). 3. Diethyl ether—reagent grate (sce Notes, Caution) PROCEDURE 1. The filter paper should be brought to constant weight by washing with 75 mL of CCl, and drying at 125-130°C for 45 min. 2, Weigh 3-5 g of the ol laborarory sumple ino a.250 ml. beaker, add an equal amount of oleic acid and heat on a temperature controlled hot plate with constant stirring at 105-11 0°C uncil practically fre from water. 3. Continue the heating until the temperature reaches 118-120°C and hold at this temperature for 5 min, f the test sample does nor remain liquid on cooling, add oie acid in small amounts until the test sample remains liquid. 4, Dissolve the dehyclrated test sump in 100 mL of warm (50-55°C) CCI, (See Notes, Caution and 2) and filter through the specified filter paper. 5. Wash the residue with three 15 mL portions of 2.2% solution of oleic acid in CCl, and then with six 15 ml. portions of hot Ci, Wash again with two 15 ml portions of diethyl ether (see Notes, Caution) or until che reside is Fee from oil. Make certain that che cop ofthe filter is choroughly washed and free from any ol. 6 Transfer the last races of any residue remaining in the beaker to the filter by allowing the solvent to evaporate when che salts become fice flowing. 7. Dry the residue at 125-130°C on the flter paper for 45 min, cool in a desiccator and weigh. ‘Note—If ammonium salt are present, do not proceed with the ignition in Procedure, 8. Dry at 125-130°C for 45 min and repeat to constant weight 8, In the absence of ammonium salts, transfer the filter paper with residue to a tared crucible, ignite at a dull red heat (600-550°C) for 15 min, cool in a desiccator to room temperature and weigh. Repeat the ignition until constant weight is obtained (see Notes, 1). ‘Note—The ignition should be carried out in a propedly operating fame hood. ‘CALCULATIONS 1. When ammonium ss are presert— Inorganic suifies and chlorides, including ammonium sats, 9 = °F died residue oy toa oes porn 2. When arumoniam sk re abtent— a of ged side. Nonvoail inorganic suites an chords, 5 = Si ‘ras oft portion 100 Noes Caution Carbon tetrachloride is known carcinogen. Is toxic by ingestion, inhalation and skin absorption, causing irritation, headaches and nausea on mild exposure. More severe exposure can lead to liver and kidney damage. It isa narcotic. Ie should not be used ro ‘tinguish fires. Ie decomposes to phosgene gas at high temperature. The TLV is 5 ppm in air. A fume hood should be used at al times when using carbon tetrachloride. Page 1 of 2 TRANS OF SULFONATED AND SULFATED OS F 6-44 « Inorganic Salts Diedhyl ether is highly flammable and is a severe fire and explosion hazard when exposed to heat or flame. Iti a central nervous system depressant by inhalation and skin absorption. It will form explosive peroxides upon exposure to light, Handle empty containes, particularly those from which ether has evaporated, with extreme caution. Explosive limits in air are 1.85-48%. ‘The TLV is 400 ppm in ait A fume hood should be used ac all times when using diethyl ether. NUMBERED NOTES 1 In the abvence of ammonium silts, the difference berween the percentage of the dried residue and the percentage of the ignite residue shall noc be greater than 0.25%. 2, 11.1 Trichloroethane (TCE) has been suggested a a replacement for carbon tetrachloride in this method. Although TCE is a halogenated hydrocarbon, the TLV (350 ppm) is ess than those of chloroform, carbon tetrachloride and methylene chlo fide. ( yelohexane and isooctane may also be considered as alternate solvents. These solvents have not been collaboratively ‘nudied » thin the AOCS technical committees. This recommendation does not represent official approval by the AOCS Uniform Methods Committee Page 2 of 2 ANALYSIS OF SULFONATED AND SULFATED O1LS AOCS Official Method F 7-44 Rezpproved 2000 Total Alkalinity DEFINITION This method determines the tral alkalinity of the fixed alka, ammonia, and triethanolamine which are bound as soap: fee alll; and the allalinity of iraableallaline sls, but not that of non-ttatable alkaline sls. SCOPE Applicable co sulfonated and sulfite oils APPARATUS 1. Erlenmeyer flask—250 or 300 mL, with glas stopper. REAGENTS 1. Sodium hydroxide (NaOH) solution, 0.5 M—aceurately sandardized (sce AOCS Specification Ht 12-52 For procedure) (see Notes, 1) 2, Sulfuric acid (H,SO.) solution, 0.25 M—accurately standardized (See AOCS Specification H 13-52 for procedure). 3. Diethyl ether—feagent grade (sce Notes, Caution). 4, Sodium chloride (NaCl)—reagene grade. 5. Methyl orange indicator—0.1% in distilled water. PROCEDURE 1, Weigh 10 g of laboratory sample inco an Erlenmeyer flask and add 100 ml. of distilled ware, Warm gently, if necessary, 9 promote solution. Cool to room cemperature and add 30 g of NaCI, 25 mi. of diethyl ethes, and 2 or 3 drops of indicator Note—This procedare should be cartied out in a properly operating fume hood 2. Add 0.25 M H,SO,, several drops aca time, shaking gently until the mixtute is slightly acid. Add 0.5 M NaOH, several drops ata time, and shake vigorously until the solution is allaline, 3. Back-titrare with acid, 1 or 2 drops ata time until the end point is reached, shaking vigorously after each addition. Wait 3 min before reading the burettes. CALCULATIONS, 1. Total alkalinity as mg KOH/g = Where— B = volume, mL of 0.25 M acid C= volume, mL of 0.5 M alkali (B-)x 28.05 ‘mas of tex portion, g NOTES Caution Follow the precautions for handling sodium hydroxide and sulfuric acid as noted in AOCS Specifications H 12-52 and 113-52, Diethyl ether is highly flammable and isa severe fire and explosion hazard when exposed to heat or flame. It isa central ner- vous system depressant by inhalation and skin absorption. Ie will Form explosive peroxides upon exposure to light. Handle empty containers, particularly those from which ether has evaporated, with extreme caution. Explosive limits in ar are 1.85-48%. The TLV is 400 ppm in air. A fame hood should be used a all rimes when using diethyl ether. Sulfuric acid isa strong acid and wil cause severe burns. Protective clothing should be worn when working with this acid. Ie isa dehydrating agent and should not be stored in the vicinity of organic materials. Use great caition in mixing with water due ‘to heat evolution that can cause explosive spattering. Always add the acid co water, never the reverse. NUMBERED NOTES 1. Although sodium hydroxide is used in the procedure, results are expressed based on mg KOH/g, The factor used in the ‘calculation i based on the face that 1.0 mL of 1.0 M NaOH solution is equivalen to 56.1 mg of KOH or 1,0 mL of 05 M NiOH solution is equivalent 10 28.05 mg of KOH. If the normalities of the acid and/or alkali solutions are not exactly 0.5 M, the values for mL. (B and C in the calculation) can be ealeulated on the basis of 0.5 M, e.g, 10.0 mL of 0.45 M NaOH is equivalent co 9.0 ml. of 0.50 M NaOH, Page 1 of 1 ~ ANALYSIS OF SULFONATED AND SULFATED OILS. AOCS* AOCS Offical Method F 8-44 Total Ammonia p_—__ DEFINITION This method determines rotal ammonia in the laboratory sample. SCOPE Applicable to sulfonated and sulfated oils APPARATUS. 1. Beaker—500 mL. 2, Erlenmeyer flask—250 mL, with glass stopper, REAGENTS: 1. Sodium hydroxide (NaOH) solution, 0.5 M—accurately standardized (see AOCS Specification H 12-52 for procedure) (see Notes, 1). 2. Sulfuric acid (H,SO,) solution, 0.25 M—accurately standardized (see AOCS Specification H 13-52 for procedure). 3. Methyl orange indicstor—0.1% in distilled water. 4. pH paper. 5. Sodium chloride (NaCl) —reagent grade. 6. Diethyl ether—reagent grade (sce Notes, Clsuzion), PROCEDURE 1. Tora alkaliniey— (a) Determine the coul alkalinity as directed in AOCS Official Method F 7-44 Allalinity ater boiling— (2) Weigh 10 g of laboratory sample into a 500 mL beaker and add 100 mL of distilled water. Add 25 mL of 0.5 M NaOH and boil for 30 min or until all che ammonia is expelled Test with moistened pH paper. (6) Cool, add 2 oF 3 drops of indicator, and titrate co an approximate end point. Transfer the concent toa glas-toppered flask and add 30 g of NaCl and 25 mL. of diethyl ether. ‘Note—This procedure should be carried out in a properly operating fume hood. 3. Titrate tothe same end point as in the titration of total alkalinity in Procedure, 1, a, Stopper the flask and shake thoroughly several times during the titration, Wait 3 min before reading the buretces. CALCULATIONS 1, Total ammonia, % = 0.0303 T Where— +(B-C) x 28.05 ‘mas of tex portion, g A = otal alkalinity in mg KOH/g from Procedure, Ia B= volume, ml. of 0.5 M alkali added C= yolume, mL of 0.25 M acid added 0.0303 » molecular ratio of NH,/KOH NoreEs Caution Follow the precautions for handling sodium hydroxide and sulfuric acid as noted in AOCS Specifications H 12-52 and 113.52. Diethyl ether is highly flammable and isa severe fire and explosion hazard when exposed to heat or flame. Iisa central ner- vous system depressant by inhalation and skin absorption. Icwill form explosive peroxides upon exposure to light. Handle empty containers, particulatly those from which ether has evaporated, with extreme caution, Explosive limics in airare 1.85-4896. The TLV is 400 ppm inait. A fume hood should be used at all times when using diethylether. Sulfuric acid isa strong acid and will cause severe burns. Protective clothing should be worn when working with this acid. Tt is a dehydrating agenc and should not be stored in the vicinity of organic materials. Use great caution in mixing with water due to heat evolution thar can cause explosive spaticting, Always add the acid 0 water, never the reverse, Page 1 of 2 ‘ANALYSIS OF SUIFONATED AND SULFATED O1S F 8-44 * Total Ammonia NUMBERED NOTES 1, Although sodium hydroxide is used in the procedure, results ate expressed based on mg of KOH/g. The factor used in the calculation is based on the fact that 1.0 mL of 1.0 M NaQH solution is equivalent to 56.1 mg of KOH or 1.0 mL of 0.5 M NaOH solution is equivalent to 28.05 mg of KOH. If the normalities of the acid andor alkali solutions are not exactly 0.5 M, the values for mL (B and C in the calculation) can be calculated on the basis of 0.5 M, eg. 10.0 mL of 0.45 M ‘NaOH is equivalent to 9.0 mL of 0.50 M NaOH. Page 2 of 2 [ANALYSIS OF SULFONATED AND SULFATED OILS AOCS AOCS Official Method F 92-44 Reaperoved 2009, Acidity, Method A DEFINITION ‘This method determines free (uncombined) faty acids, which are calculated in terms of mg of KOH neces- sary co neutralize the fatty acids in 1g of rest sample. SCOPE Applicable to sulfonated or sulfated oils except in the presence of ammonium ot triethanolamine soaps or salts or other compounds which do not react neutral co phenolphthalein when dissolved in alcohol. APPARATUS. 1, Erlenmeyer flask—250 mL. 2. Bureite—Class A, 50 mL. REAGENTS 1. Diethyl ether—reagent grade (see Notes, Caution). 2. Eshylalcohol—95% (SDA Formulas 30 and 3A are permitted). Add 2-3 drops of phenolphthalein indicator solution and neutralize with alkali co a faint, bue permanent pink color, just before using, 3. Phenolphthalein indicator—1% in 95% ethyl alechol. 4, Sodium hydroxide (NaOH) solution, 0.5 M—accurately standardized (sce AOCS Specification H1 12-52) (see Notes, 1) PROCEDURE 1. Weigh 10 g of test sample into an Erlenmeyer flask andl add 50 ml. of neutralized alcohol, 25 mL of diethyl ether, and 5 drops of phenelphehalein indicat. 2. Tierate with the standardized NaOH solution until a pink color persists after shaking vigorously for 30 sec CALCULATIONS 1. Acidity as mg KOH/g = “lume: ml. of alkali x 28.05, ‘mass of test portion, g Notes Caution Follow the precautions for handling sodium hydroxide as noted in AOCS Specification H 12-52. Diethyl ether is highly flammable and is a severe fire and explosion hazard when exposed to heat or flame. It is a central nervous system depressant by inhalation and skin absorption. [twill form explosive peroxides upon exposure to light. Handle empty containets, particularly those from which ether has evaporated, with extreme caution, Explosive limits in air are 1.85-48%. “The TLY is 400 ppm in air. A fame hood should be used at all times when using diethyl ether NUMBERED NOTES 1. Although sodium hydroxide is used in the procedure, results are expressed based on mg of KOH/g, The factor used in the saleulation is based om the fact that 1.0 mL. of 1.0 M NaOH solution is equivalent to 56.1 mg of KOH or 1.0 ml of 0.5 M NaOH solution is equivalent to 28.05 mg of KOH. Ifthe normality of the alkali solution is not exactly 0.5 M, the value for ml. of alkali in the calculation can be calculated on the basis of 0.5 M, eg. 10.0 mL. of 0.45 M NaOH is equivalent co 9.0 mL of 0.50 M NaOH. Page 1 of 1 ANALYSIS OF SULFONATED AND SULFATED OMS AOCS Official Method F 9b-44 Acidity, Method B pe EFINITION This method determines the free (uncombined) fatty acids, which are calculated in tetms of mg of KOH necessary to neutralize the faty acids in 1g of test sample SCOPE Applicable co dark colored sulfonated or sulfited oils, except in the presence of ammonium or trietha- nolamine soaps. APPARATUS 1. Erlenmeyer flask—250 mL, with glass stopper. 2. Burette—Class A, 50 mL, REAGENTS: 1. Sodium chloride (NaCl)—reagent grade. 2. Diethyl ether—reagent grade (ace Notes, Caution) 3. Phenolphthalein indicator—1% in 95% ethyl alcohol. 4, Ethyl aleoho!—95% (SDA Formulas 30 and 3A are permitted). Add 2-3 drops of phcnolphthalein indicator solution and neucralize with alkali toa faint pink color just before using. 5. Sodium hydroxide (NaOH) solution, 0.5 M—accurately standardized (sce AOCS Specification H 12-52 for procedure) (Gee Notes, 1). PROCEDURE 1, Weigh 10 of west sample into Erlenmeyer flask containing 100 mL of distilled water. Warm, if necessary, to promote sokie tion. Cool and add 30 g of NaCl, 25 ml. of diethyl ether, and 50 ml. of neutralized alcohol 2. Add 5 drops of indicator and arate with 0.5 M NaOH until dhe fise pink tinge appears inthe water layer. Shake vigorously afer each addition of alkali CALCULATIONS. lume, mL of alkali x 28.05 1. Acidity as mg KOH. muss of test po Notes Caution Follow the precautions for handling sodium hydroxide as noted in AOCS Specification H 12-52. Diethyl ether is highly flammable and isa severe fire and explosion hazard when exposed to heat or flame. It sa central ner- ‘vous system depressant by inhalation and skin absorption. Iwill form explosive peroxides upon exposure o light. Handle empty containers particularly chose from which ether has evaporated, with extreme caution, Explosive limits in air are 1.85-48%, The ‘TLV is 400 ppm in air. A fume hood should be used a all times when using diethyl ether. NUMBERED NOTES 1. Although sodium hydroxide is used in the procedure, results are expressed based on mg of KOH/g, The factor used in the caeulation is based on the fact tha 1.0 mL of 1,0 M NaOH solution is equivalent o 56.1 mg of KOH or 1.0 mL of 0.5 M NOH solution is equivalent to 28.05 mg of KOH. Ifthe normality of the alkali solution is not exactly 0.5 M, the value form of alkali in the calculation can be calculated on the basis of 0.5 M, eg, 10.0 mL of 0.45 M NaOH is equivalent to 9.0 ml. of 0.50 M NaOH Page 1 of 1 ANALYSIS OF SULFONATED AND SULFATED OILS. AOCS Official Method F 9c-44 Reapproved 2009 Acidity, Method C DEFINITION ‘This method determines the free (uncombined) fatty acids which are calculated in terms of mg of KOH necessary to neutralize the fatty acids in 1 g of tes sample. SCOPE Applicable to sulfonated or sulfated ols in the presence of ammonium ot triethanolamine soaps, or both. ‘APPARATUS 1, Exlenmeyer flask—250 mL. with glass stoppet. 2. Burette—Class A, 50 mL. REAGENTS, 1. Sodium hydroxide (NaOH) solution, 0.5 M—accurately standardized (see AOCS Specification H 12-52 for procedure) (see Notes, 1). * 2. Ethyl alcohol-—95¢6 (SDA Formulas 30 and 3A are permitted). Add 2-3 drops of phenolphchalein indicator solution and neutralize with alkali co a fain, but permanent, pink olor just before using 3. Phenolphthalein indicator—196 in 95% ethy] alcohol. 4, Sodium chlotide (NeCl) solution—saturated in disilled water. PROCEDURE 1, Total alkalinity — (2). Determine the rota alkalinity as directed in AOCS Official Method, F 7-44. 2. Free- and alkali-combined fatty acids— (@) Proceed as directed in AOCS Official Method, F 2b-44, Procedure, 1, for separation of purified ol. Noten the presence of acetates, wash the diethyl ether (see Noes, Caution) layer carcfully with saturated NaCl solution until the wash water is neutral to phenolphthalein when | or 2 drops of 0.5 M NaOH are added. (b) Add exactly 0.5 mL of 0.5 M NaOH to the extract and evaporate the diethyl ether (see Notes, Caution) to a total volume 0f 25 mL. Add 50 mL of neutral alcohol and titrate the mixture with 0.5 M NaOH to faint, but permanent pink color Include the intial 0.5 ml. of 0.5 M NaOH in che mL. of 0.5 M NaOH required in the titration CALCULATIONS: 1. Acidity as mg KOH, Where— A= otal alkalinity feom AOCS Official Method, F 7-44 volume, ml NaOH? x 28.05 ‘mas of text portion (Ba) ‘ml. NaOH as required in titration in Procedure, 2, b, NorEs Caution Follow the precautions for handling sodium hydroxide as nored in AOCS Specification Hi 12-52, Follow the precautions noted in AOCS Offical Method, F 2h-44 for the safe handling of diethylether. NUMBERED NOTES 1. Although sodium hydroxide is used in the procedure, result are expressed based on mg of KOH(/g, The factor used in the calculation i based on the fact that 1.0 mL of 1.0 M NaOH solution is equivalent to 56.1 mg of KOH or 1.0 mL. of 0.5 M NaOH solution is equivalent to 28.05 mg of KOH. If che normality of the alkali solution is not exactly 0.5 M; the value for mL. of alkali inthe calculation can be calculated on the basis of 0.5 M, eg., 10.0 mL of 0.45 M NaOH is equivalent to 9.0 mL of 0.50 M NaOH. Page tof ANALYSIS OF SULFONATED AND SULFATED OILS KOCS & AOCS Official Method F 10-44 Reapproned 2009 Water-Immiscible Organic Solvents DEFINITION ‘This method determines water-immisible organic solvents that are volatile with steam (see Notes, 1-4). SCOPE Applicable co sulfonated and sulfated oils that do not contain volatile compounds that are mutually soluble ‘APPARATUS 1. Glas distillation apparatus, constructed as shown in Figure 1, with the following specifications — (a) Flask—500 mL, short-nece, round-bottom type. (b) Condenser—water-cooled. (©) Traps for solvents heavier than water—constructed of well-annealed glass and graduated to contain 5 mL. at 20°C. Ie shall be subdivided into 0.1 mL. divisions with each 1 mL line numbered and the 5 mL line atthe top. The error at any indicated capacity shall not exceed 0.05 mL. (4) Traps for solvents lighter than water—constructed of well-anncaled glass and graduated to contain 5 mL at 20°C. Ie shall be subdivided into 0.1 mL divisions with each 1 mL line numbered and the 5 mL. line atthe top. The error at any indicated capacity shall noc exceed 0.05 ml. 2. Heat source—an electric hot plate with a suitable means of control. 3. Glass beads or pumice stone. REAGENTS. 1. Sodium (NaOH) or potassium hydroxide (KOH) solution —approximately 1M. 2. Phenolphthalein crystals. 3 re (Na,CO,)—reagent grade. 4G lc (CaCl, )—reagent grade 5. Xylene—reagent grade (see Notes, Caution) 6. Oleic acid USP grade or equi PROCEDURE 1. Calibration of receivers— (@) For solvents heavier than wate, calibrate the receiver by the following procedure—add about 1 g of distilled water to a mixture of 80 g of xylene and 10 g of oleic acid. Conduct the distillation a8 described in AOCS Official Method F Lad4, Calibrate the receiver up co its maximum capacity at intervals of | mL. ©) For solvents lighcer than water, calibrate the receiver by the following procedure—insert a one-hale stopper containing a short piece of glass rubing into the lower opening ofthe trap. Attach a separatory funnel to the lass tube by means of rubber tubing. Fill he funnel with some liquid heavier than and non-miscible with water, open the stopcock and aise the funnel carefully until che liquid flows into che receiver to approximately the 0.3 mL matk. Introduce exacdy 1 mL ‘of water with a pipet into the graduated arm followed by a drop of pine oll to protect the surface from evaporation, Measure the volume ofthe water in che tube. Raise the level ofthe solvent in the graduated cube. Continue inthis man. ner until the entre tube has been calibrated. 2. Introduce 50 mL of distilled water into the distillation flask and a sufficient amount of the test sample to yield about 4 mL ‘of solvent. This is conveniently done with a weighing bottle. IF highly volatile solvents are suspected of being present, iis preferable to remove the top of the weighing bortle and to drop che bottle and contents into the distillation flask. If caespic acid is present, che size of test sample should be such as to yield about 2.5 mL of solvent. If cresylic acid is present, add about 1.5 mL. of pine il, exactly weighed, to the distillation flask to reduce the gravity ofthe distillace. 3. Rapidly neutralize che solution in the distillation flask with either NaOH or KOH, approximately 1 M, until slightly allaline to phenolphthalein, added as crystals. Add 2 g of Na,CO,, enough CaCl, to prevent foaming (usually 3-5 g) and a few glass beads or pumice stones to prevent bumping 4 Attach the resive othe condenser and fil he ever with water by pouring though the condense. mmediaelyavach the distillation flask and begin the disillaion, 5. Heat at such a rate that refluxing will start 7-10 min fier the heat is applied, the water being at room temperature inital, Read the volume of solvent collected in the receiver 2 hi after refluxing starts and every hour thereafter until the esis complete ‘The testis complete when the volume of solvent increases by no more than 0.1 ml. in any ewo consecutive 1 hr periods, The source of heat is removed from the distillation flask and the fask cooled for exactly 3 min before raking readings. The distla- tion is continued for an additional 15~30 min withthe water in the condenser tube emptied as an additional precaution, Page 1 of 3 “ANALISS OF SULTONATED AND SULFATED OWS F 10-44 * Water-Immiscible Organic Solvents 6, Aficr completion of che test, allow the receiver to stand for a least 40 min in order to cool co 1o0m temperature and to allow the distillate ro become elear and then read the volume of solvent. 7. Remave about 2.5 mL of solvent from the receiver with a pipet and determine the specific gravity (sp. gt) in a 2 mL, pycnometer Tn the case of solvents heavier than water the Former is separated by means ofa small separatory funnel CALCULATIONS \Wacer-immiscible organic solvents, % = Where ddetcriived in Procedure, 7. {mass of solvent ~ mass of pine oil! mass of test portion x 100 rat = (total mL distilled x sp. gr") Nores Canc Rpleuc i lameusle anda dangerous fire risk. The TLY is 100 ppm in at NUMDERED NOTES Ty lithe puescu of watersmiscible solvents (auch as alcohol) that are also miscible with water-immiscble solvents, some of the former will b> found in the solvent layer. When there is an appreciable difference in the boiling points and specific eravcies, cl the two (p07 of solvents, they may be separated qualitatively by fractional distillation and the specific gravities of the fractions deve-mined, from which, together with the specific gravity of the solvent layer, the amount of water-immiscible solves may be calculated 2. In the ase of pine oil or cresylic acid mixed with alcohol, the alcohol may be volailized by heating over a hot plate with count sot ster, to a temperature of about 150°C, after which the specific gravity of the residue is determined. The quantity f she wares immiscible solvent may now be calculated as in Notes, 1. This method may be applied co all such mixtures ‘oheie there is considerable difference in boiling points and specific gravities and the specific gravity of one ofthe solvents 3, Wher tore adifference in the specific gravitis, but not in the boiling points, andthe specifi gravity of the wacer-miscible solvents is known, che warer-immiscible solvent is extracted with diethyl ether over water, the ether evaporated, and the spe- Gh saavty othe residue determined. In this procedure, icis assumed thatthe boiling point of the water-immiscible solvent is considerably higher than that of ether, In all other eases, to obeain che warer-immiscible solvent, ic will be necessary t0 ntitative fractional distillation or to chemical means. resort 03 4 4, Wid ose portions yielding distillares that are both heavier and lighter than water, the disilacon i ise made with dhe ap for solvents heavier than water and, after flushing all the solvent floating on top of the water layer back into the distillation flask sas tating che trap for solvents lighter chan water, the distillation is continued to completion. Page 2 of 3 ‘ANALYS OF SULFONATED AND SULIAED OS F 10-44 + Water-Immiscible Organic Solvents S240 22-24 meni 235-240 mm ott mmis. | Capacity 5 mt, reduatod 0.1 mL, 2449 Capacity § ml, | SOTO mm raduated in 0.4 mL, ‘rap fr solvens lighter than water Figure 1. Apparatus for water-immiscible organic solvents, Page 3 of 3 OFFICIAL METHODS AND RECOMMENDED PRACTICES OF THE AOCS Sampling and Analysis of ~ Soapstock These methods are applicable, within the scope indicated with each method, to the sampling, and analysis of soap stock obtained from the refining of fats and oils of animal, vegetable and marine origin. These methods have been developed through extensive collaborative work feWhile these methods are provided primarily for the commercial evaluation of soap stock for ading purposes, they are equally well suited to quality conteol or research analysis WARNING Some of the methods contained in this section require the use of flammable, toxic, haz- ardous and/or poisonous materials. Manufacturers’ safely instructions and the cautionary statements included in the methods for handling these materials should be observed Methods requiring the use of hazardous and toxic materials should be carried out in a prop- erly operating fume hood, to prevent expostre of laboratory personnel. Appropriate protec. tive clothing and equipment should be used. See the Laboratory Safety section of this book. cae SAMPLING AND ANALYSIS OF SOAPSTOCK. AOCS AOCS Official Method G 1-40 Reapproved 2009 Sampling SCOPE Applicable to raw and acidulated soapstock from all types of fas and cil. APPARATUS: 1, Metal drum, can or other container with tight fitting coverat leas 1.50 L (120 Ib) capacige 2 Ladle with handle 5. Sample cans with righ ising covers 500 or 1000 mL (1 ox 21) eapaciy. PRESERVATIVE 1. Oil of cassia PROCEDURE 1. Raw soapstock is sampled as itis loaded, because filled or partly filled tank cars, drums, or barrels cannot be properly sampled after standing for any length of time. Acidulated soap stock may be sampled by this method or by any of the methods speci- fed for oils ot liquid fats as directed in ACS Official Method, C 1-47. The test sample is draw from the flowing stock ar the discharge end of th pipe, as the material enters the ear or other container 2, Take rest samples with the ladle From the flowing stock at regular and frequent intervals, so that not les than 25 individual portions of uniform size ate collected. 3. Place these portions in a drum, can or other metal container with tight fitting cover. Keep the container tightly covered, except during the actual simpling, so as to prevent the loss of moisture and to prevent contamination with Water or other foreign material. This is particularly eruc if the flow is interrupted for any reason ‘Ceution—IF the flow is interrupted and itis necessary to clear the lines, air is preferable to steam. [fit becomes necessary ‘o blow the line with steam, the steam must be blown back ftom the discharge end of the line into or towards the supply tankand nor towards the sampling end of the line. 4, The total laboratory sample accumulated shall amount to 0.1-0.2%6 by weight of the product sampled, ie 25-50 L (60-120 Ib) per tank cat 5. Add 0.1% of oll of casia to the composite test sample of raw soapstock (not acidulated stock), mix thoroughly, fill four 500 g-1 eg (1 or 21b) cans and seal them hermetically. The cans must be plainly marked for identification. Page 1 of SAMPLING AND ANALYSIS OF SOAPSTOCK AOCS Official Method G 3-53 Reapprowed 2008 Total Fatty Acids, Oxidized Fatty Acids, Wet Extraction Method DEFINITION ‘The procedure for total fatty acids ofthis method determines the total fatty acids in the test sample, whether present as neutral or saponified oi. Any unsaponifiable fatty matter in the test sample will be included. ‘The procedure for oxidized acids ofthis method determines pettoleum ether-insoluble, but diethyl ether- soluble material, commonly referred to as oxidized faty acids, SCOPE Applicable to raw and acidulated soapstock, except from coconut, palm kernel, and similar lausie-ype ols Replaced G 3-39 APPARATUS 1. Cylinder—250 mL, glass-stoppered. 2. Erlenmeyer flask —. Filter paper—Reeve Angel no. 230, Eaton and Dikeman no. 617, or equivalent. Beaker—400 mL. 5, Separatory funnel—500 mL, glss-stoppered, 6, Soule flasks—250 mi. REAGENTS 1, Alcoholic potassium hydroxide (see Notes, Geution)— 50 g of solid KOH in 1 L of 95% ethanol, SDA formulas 30 and 3A are permitted. 2. Hyori acid (1:1) (ce Notes, Caton —Mix one volume of HC pg 1.19) wih one volameof aie wae, 5. Methyl orange indicator solution—0.1% in distilled water. 4, Petroleum ether—AOCS Specification H 2-41 (see Notes, Causion) 5. Diethyl ether—ACS grade (see Notes, Ceution). PROCEDURE FOR TOTAL FATTY ACID DETERMINATION 1. Mix the test sample thoroughly and weigh immediately. 2. Weigh 8-10 g of raw soapstock (4-5 g of acidulated soapstock) into a 300 mL Erlenmeyer flask or 400 mL. beaker (see Noes, 1). Add 50 ml of alcoholic alkali, cover with awatch glass, and heat in a water bath 0 saponify (see Notes, 2). Agitate frequently and heat for at least 30 min or until saponification is complete Remove the watch glass and continue heating in a water bath with occasional agitation to evaporate the alcohol. To avoid ‘oxidation, do not evaporate beyond a paste. If necessary, add a small amount of water when most of the alcohol has evaporated 4, Add 100 mL. of distilled water and heat until the soap has completely dissolved. Wash the contents into a glase-stoppered oplinder with hot distilled water, taking care not co exceed 2 total volume of 130 mL in the cylinder. 5. Add 3-5 drops of indicator and neutralize with dilute HCl to a pink methyl orange end point. Then add 1 mL of excess acid Rotate the cvlinder gently to mix the contents. 6. Cool to at least 35°C and acd 125 mL. of pecroleum ether. The fatty acids do not need to have separated completly before audding the ether. Stopper the cylinder, shake gently, and allow to sand until the petroleum ether layer separates. Siphon the petroleum ether layer into a 500 mL. separatory funnel, making sure chacas lite as possible ofthe insoluble matter which gathers a the ether-wate interface is carried over ino the separatory funnel. If any appreciable amount of insoluble matter does siphon aver into the separatory funnel, it will usually sete to the bottom and can be drained back into the extraction cylinder, Make at least four more similar extretions, using 25-30 ml. of petroleum ether each time and shak- ing the cylinder vigorously for 30 sec with each extraction, Extractions should be continued unci the petroleum ether layer is practically colocless. Save the acid water in the extraction cylinder iF oxidized fatty acds are co be determined {as noted in the next Procedutc). 8, Dilure the combined extracts with petroleum ether ro 450 mL and mix dhoroughly by gently shaking the separacory fannel 9. Filter the diluted petroleum ether in a water bath as necessary to permie collection ofall che extracts and subsequene wash- ings. Wash the filter paper thotoughly with about 75 mL of petroleum ether, caking care to remove the yellow ring of fatty acids which usualy forms near the upper edge ofthe filter paper. This is best accomplished by washing the paper while its upper edge is lifted away from the filtering funnel with a small spatula or tweezers. Page 1 of 2 TERIPING AND ANATSIS OF SOAPSTOCR G3-53 © Total Fatty Acids, Oxidized Fatty Acids, Wet Extraction Method 10, Evaporate the petroleum ether in a waterbath under 2 gentle stream of clean dry air, Finally, dry the fay acids in an ait oven at 10 + 2°C (0: 30 min. Cool in a desiccator to ambient temperature and weigh. Repeat until constant weight is acained. ‘Constant weight is attained when the loss or gain in weight does not exceed 0.1% in successive 30 min drying periods. This is the weight of total fatry aids. PROCEDURE FOR OXIDIZED ACID DETERMINATION 1. Add 25-30 mL of diethyl ether to contents of the cylinder ater Procedure, 7 for total fatty acids, stopper, shake gently, and allow io stand uncil the diethyl ether layer separates. 2. Siphon the diethyl ether layer through the same filter paper used previously into another tared 250 mL Soxhlet flask which has heen dried and cooled in a desiccator. Make at lease four similar extractions using 25-30 ml. of diethyl ether each time, ant slike the eylinder vigorously for 30 see with each extraction. The last diethyl ether extract should be practically colorles: 3, Fler all exracts through the same filer paper and finally wash this ter paper thoroughly with diethyl ether to recover all of the oxidized acids 4 Tho sovate diethyl ether im a fame hood in a water bath under a gentle stream of clean dry air Finally dry the oxidized fay acid. 0 an air oven at 105 # 2°C for 30 min. Cool in a desiccator to ambient temperature and weigh. Repeat unt consans weight i attained, Constant weight is attained when the loss or gain in weight does noc exceed 0.1% in successive 30) min ciyiny periods. This s the weight of oxidized fatty acids. CALCULATIONS, 1, Total Farry Acids, % 2, Onidized Fatey Acids, 99 = Bas of onidine’ Buy 228 199 NOTES Causion When working with cxttemely caustic materials like potassium hydroxide, always add pellets to water and not the reverse. Alkalies ane extrem niic when mixed with water. Take precautions to contain the caustic solution in the event the mixing con- tains brs foun ce extreme heat generated ‘Wher diltting acids, always add acid to water unless otherwise directed in a method. Keep acids off skin and protect eyes, when, working wits acids. IFasids come in contact with skin or eyes, wash immediately with large amounts of water. Petroleum rticr is extremely flammable, Avoid static electricity. The explosive limits in air are 1-6%, A fume hood should bbe used at all smics when using petroleum ether. Diethyl ether is highly flammable and is a severe fire and explosion hazard when exposed to heat or fame. It isa central ner- vous system dep sit hy inhalation and skin absorption. Ie will form explosive peroxides upon exposure to light. Handle empty Container particularly those from which ether has evaporated, with extreme caution. Explosive limits in air are 1. 85-48%. The TLV is 400 ppim in air. A fume hood should be used ac all simes when using diethylether. Tiydiochi coil isa strong acid and will cause severe burns, Protective clothing should be worn when working with this acid, Its toxic by ingcstion and inhalation and a strong itrcane to eyes and skin. The use ofa properly operating fume hood is recorime)ded. When diluting the acid, always add dhe acid to che water, never the reverse. NUMBERED NOTES T. On ta scapsiock iv is advisable co weigh the test portion into the beaker or Erlenmeyer flask from a weighing bote, because 2! joss moisture rapidly. Because a 400 mL. beaker is bulky to weigh on an analytical balance, itis advisable to 2» «id acidulated test portions from a weighing bottle when a beaker i use. 586 ethanol and 2-3 g of solid KOH may be used instead of the alcoholic solution, if desired. Page 2 of 2 SAMPLING AND ANALYSIS OF SOAPSTOGK AOCS& AOCS Official Method G 4-40 eapprvei09 Total Fatty Acids pe DEFINITION This method determines the roral farty acid in the test sample, whether present as neutral or saponified oil. Any unsaponifiable fatty matter inthe test sample will be included. SCOPE Applicable to raw soapstock or acidulaed soapstock from coconut, palm kernel, or other laurc-type oils. APPARATUS 1. Beakers—250 and 600 mL. Beaker or Soxhlet lask—250 mL, tared with a stirring rod. Cylinder—250 mL, glass-stoppered. Filker paper—Reeve Angel no. 230, Eaton & Dikeman no. 617, or equivalent Desiceator—containing an efficient desiccant. Calcium chloride isnot satisfactory. See AOCS Specification H 9-87. Separatory funnel—500 mL.. REAGENTS 1, Alcoholic sodium or potassium hydroxide solution—50 g of the solid caustic (sce Notes, Caution) in 1 L of 95% ethyl alcohol. SDA Formulas 30 and 3A are permitted. Hydrochloric acid (1:1)—mix (See Notes, Caution) one volume of HCI (sp. gr. 1.19) with one volume distilled water. Methyl orange indicator solution—0.19% in distilled water. - Phenolphthalein indicator solution—1% in 95% ethyl alcohol. . Petroleum ether—AOCS Specification H 2-Ai (sce Notes, Caution). sdium hydroxide solution, 1.0 M—accurately standardized and fice from carbonates (sce AOCS Specification H. 12-52) his solution should be a fre from impurities as possible in order to keep the correction at a minimum. Carbonates are che ‘usual impurities contributing to chis factor, bue other sodium salts may be present. ‘Nose—Il the presence of impurities i suspected, determine a correction factor "C” by exactly neutralizing 20 mL of the 1.0 M NaOH solution (containing a few drops of phenolphthalcin) with 1.0 M HCl solution. Evaporate che neutral slu- tion on a water bath and ghen dry for 2 hr in an air oven at 105 + 2°C. Cool in a desiccator co room temperature and weigh. Repeat until constant weight is attained. Constant weight is attained when the loss (or gain) in weight does not exceed 0.1% in successive 1 hr drying periods. Correction factor per mL of 1.0 M NaOH « sass of residue ~ 1.1691 20 PROCEDURE 1. Mis the test sample thoroughly and weigh immediately 2. Weigh an amount of tet sample which will yield about 5 g of faty acids into a 250 mL beaket. Add 50 mL. of alcoholic alkali and hicat in a water bath co saponily (see Notes 1). Cover wich a watch glass. Ser frequently and heat fora least 30 min ot until saponification is complete. 3, Remove the watch glass and continue heating in water bath with occasional titngto evaporate the echo To avoid oxidation, do not evaporate beyond a paste. If necessary, add a small amount of water when most of the alcohol has evaporated. 4, Add 100 mL of distilled water and heat until the soap has completely dissolved. Wash the contents into a glass-stoppered cplinder with hor distilled wate, taking care not to exceed a volume of 130 ml in the cylinder. 5. Add 3-5 drops of methyl orange and a small, but definite excess of dilute HCI. Rotate the eylinder gently co mix dhe 6. Cool to a least 35°C and add 125 mL of petroleum ether. The fatty acids do not have to have compleely separated before adding the petroleum ether. Stopper the cylinder, shake gently, and allow to stand uel the petroleum ether layer separates, 7. Siphon the petroleum ether layer through a filter paper into a 600 ml. beaker oF separatory funnel. If this extract is loudly. ic should be refltered, but any subsequent cloudiness may be disregarded. 8, Make at least four more similar extractions using 25-30 mi. of petroleum ether each time and shake vigorously for 30 sec with each extraction 9. Filter each extract thtough the same filter paper asthe first and finally wash this filter paper thoroughly with petroleum ether to remove all of the fatty acids. Page 1 012 SAMPLING AND AVALSIS OF SOAPSTOCR G 4-40 © Total Fatty Acids 10. Evaporate the petroleum ether in a fume hood in a water bath under a gentle stream of clean dry ait to a volume of 50-75 ml. Add $0 mL of neutral ethyl alcohol and 0.5 ml. of phenolphthalein. Titrate with 1.0 M NaOH solution to the first permanent pink color. 11. Evaporate che remaining petroleum ether and concentrate the solution in a water bath under a current of clean dry air uncl the volunic » icluced to about 25 mL. 12, Use hot ethyl alcohol to transfer into a 250 ml beaker or Soxhlet flask which has been dried, cooled in a desiccatos, and tared cha stirring rod. 13, Complete she evaporation and then dry in an air oven at 105 + 2°C for 2 hr. Cool in a desiccator to ambient temperature ‘and weigh. Repeat drying for 30 min intervals until constant weight is obtained, Str the mass occasionally while evaporating, and dry ng. C nstant weight is attained when the loss (or gain) in weight does not exceed 0.196 in successive 30 min drying periods CALCULATIONS ‘w(0.022+C)T] ‘mas of text portion 1, “Total Farty Acids, % x 100 Where sys: of sodium soap from Procedure, 13, ‘-s

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