1、Designation: D1065 96 (Reapproved 2014)1Standard Test Method forUnsaponifiable Matter in Naval Stores, Including Rosin, TallOil, and Related Products1This standard is issued under the fixed designation D1065; the number immediately following the designation indicates the year oforiginal adoption or,
2、 in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1NOTENote 1 was added editorially in July 2014.1. Scope1.1 This test method covers the deter
3、mination of the per-centage of material in Naval Stores products as defined inTerminology D804 including rosin, tall oil and relatedproducts, other than insoluble dirt or similar visible foreignmatter that does not yield a water-soluble soap when thesample is saponified with potassium hydroxide.1.2
4、The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-pr
5、iate safety and health practices and determine the applica-bility of regulatory limitations prior to use.NOTE 1It has been reported that this method may not be applicable togum rosin, especially any gum rosin containing volatile terpenes. Volatileterpenes are by definition unsaponifiable matter, and
6、 can be lost under thedrying conditions described in 8.4. The method is applicable to tall oilrosin and wood rosin as these rosins do not contain volatile terpenes.2. Referenced Documents2.1 ASTM Standards:2D509 Test Methods of Sampling and Grading RosinD803 Test Methods for Testing Tall OilD804 Ter
7、minology Relating to Pine Chemicals, IncludingTall Oil and Related ProductsE177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Significance and Use3.1 This test method is designed
8、to broaden the scope of theprevious edition of the test method by the inclusion of tall oiland tall oil derived from products as test materials. TestMethods D803 currently includes a method for the determina-tion of unsaponifiable matter.3.2 The amount of unsaponifiable matter in tall oil and otherr
9、elated products is important in characterizing such products asit indicates the level of nonacidic material, both free andcombined, present in the test material. The unsaponifiable innaval stores products is primarily composed of higher molecu-lar weight alcohols, sterols, and hydrocarbons.4. Appara
10、tus4.1 Erlenmeyer or Other Flat-Bottom Flask, of 125-mL to250-mL capacity, with standard-taper 24/40 joint.4.2 Erlenmeyer Flask, of 250-mL to 300-mL capacity, withwide mouth.4.3 Separatory Funnels, of 300-mL to 500-mL capacity,with glass or polytetrafluoroethylene (PFTE) stoppers.4.4 Graduated Cylin
11、der, one of 10 to 25-mL and one of 50to 100-mL capacity.4.5 Beaker, of up to 250-mL capacity.5. Reagents5.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analyt
12、ical Reagents of the American Chemical Society,where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit use without lessening theaccuracy of the determination.1This test method is under the jurisdictio
13、n of ASTM Committee D01 on Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D01.34 on Pine Chemicals and Hydrocarbon Resins.Current edition approved July 1, 2014. Published July 2014. Originally approvedin 1949. Last previous edition approved in
14、2010 as D1065 96 (2010). DOI:10.1520/D1065-96R14E01.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Reagent
15、Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand Nat
16、ional Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States15.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean distilled, or deio
17、nizedwater.6. Preparation of Sample6.1 Procurement and handling of samples will vary depend-ing upon the physical state of the material. In all instances, thesampling should conform to accepted sampling techniqueswhich ensure the sample is representative of the material beingsampled.6.2 Uniform liqu
18、id material should be mixed well and analiquot removed for analysis. Titer in fatty acid samples shouldbe resolubilized by gentle heating and agitation. Rosin crystal-lization in liquid samples, such as distilled tall oil (DTO),should be resolubilized by heating to 160C with periodicagitation. Homog
19、eneous representative samples are impera-tive.6.3 Solids that melt at relatively low temperature (that is,tall oil pitch) should be warmed to liquification to facilitatemixing and pouring. Homogeneous representative samples areimperative.6.4 Solids that melt at relatively high temperatures (that is,
20、rosin) should be fractured and chipped if possible, (see TestMethods D509). The sample taken for analysis shall consist ofsmall pieces of rosin chipped from a freshly exposed part of alump of lumps, and thereafter crushed to facilitate weighingand solution. The sample shall be prepared the same day
21、onwhich the test is begun in order to avoid changes in propertiesdue to surface oxidation that is very pronounced on groundrosin having a large surface area exposed to the air.7. Reagents7.1 Alkali (titrant), Standard Alcoholic Solution (0.1 N)Dissolve 6.6 g KOH or 5.2 g NaOH, preferably in pellet f
22、orm,in 1 L of methanol (99.5 %) or ethanol (95 %) denatured byFormula No. 3A or No. 30 of the U.S. Bureau of InternalRevenue. Standardize this solution to 60.001 N using potas-sium acid phthalate, or another accepted primary standard foralkaline titrant, according to accepted quantitative practice.7
23、.2 Ethyl Ether (diethyl ether).7.3 Isopropyl Alcohol (Isopropanol) (91 to 99 %)If notneutral, make neutral to phenolphthalein by adding 0.1 N alkalisolution dropwise.7.4 Phenolphthalein SolutionDissolve 1.0 g of phenol-phthalein in 100 mL of alcohol conforming to 6.1.7.5 Potassium Hydroxide, Ethanol
24、ic (Saponification) Solu-tion (132 g KOH/L)Dissolve 132 g of KOH (preferablypellets) in 150 mL of water and dilute to 1 L with ethanol(95 %) denatured by Formula No. 3A or No. 30 of the U.S.Bureau of Internal Revenue.7.6 Thymol Blue Indicator SolutionDissolve 0.1 g ofthymol blue in 100 mL methanol (
25、99.5 %).8. Procedure8.1 Weigh 5.0 6 0.1 g (to 0.01 g) of the sample into the125-mL (250-mL) Erlenmeyer or other flat-bottom flask, usingthe 10 or 25-mL graduated cylinder add 15 mL of the ethanolicKOH solution (132 g KOH/L), attach to the condenser, andheat to reflux and maintain for 1.5 h. Remove t
26、he flask, add 30mL water, transfer to a separatory funnel, and rinse the flaskwith an additional 20 mL of water that is added to theseparatory funnel. Rinse the flask with 40 mL of ethyl ether,adding the ether rinse to the separatory funnel. Stopper andshake the separatory funnel, then allow to stan
27、d until the etherlayer separates from the water/soap layer. Drain the aqueoussoap layer (lower layer) into a second separatory funnel,allowing a few drops of the aqueous layer to remain above thestopcock to prevent loss of ether extract by creepage throughthe stopcock joint.8.2 To the aqueous soap l
28、ayer in the second funnel, add 30mL ether and extract as before. Drain the aqueous soap layerinto the original saponification flask. Add the ether layer fromthe second separatory funnel to the first separatory funnel,thereby combining the extracts. Pour the aqueous soap layerfrom the original saponi
29、fication flask into the second separa-tory funnel, add 30 mL ether and extract for the third time.Drain the aqueous soap layer from the second separatoryfunnel into the original saponification flask again, and add theether layer to the first funnel as before, thereby combining itwith the two previou
30、s extracts. Now drain off, and add to thesoap solution already in the original saponification flask, all buta few drops of aqueous soap solution that has collected at thebottom of the first separatory funnel below the combined etherextract layers. Add 2 mL of water to the first separatory funneland
31、drain off all but a few drops, combining it in thesaponification flask.8.3 Again pour the combined aqueous soap layers from theoriginal saponification flask into the second separatory funnel,add 30 mL ether, and extract for the fourth time. Afterseparation of the layers, discard the aqueous soap lay
32、er (lowerlayer) from the second separatory funnel and add the etherlayer to the combined ether extracts in the first separatoryfunnel. Carefully drain off any remaining aqueous soap layerthat may have collected above the stopcock under the etherextracts in the first separatory funnel. Add 2 mL of wa
33、ter, swirlthe separatory funnel gently, allow the water to settle, and thendrain off and discard the water layer (lower). Repeat thiswashing once with 5 mL of water, followed by three washeswith 30 mL of water. Drain a portion of the third 30-mL waterwash into a beaker, add 2 drops of phenolphthalei
34、n solution,and examine for any pink color. If pink color is observed, washonce more with 30-mL water. The absence of pink colorindicates the wash is neutral to phenolphthalein.8.4 Drain the neutral washed, combined ether extracts into adry, tared (to 0.001 g or 0.0001 g), wide-mouth Erlenmeyerflask,
35、 rinse the separatory funnel with 15 mL ether and add thisto the tared Erlenmeyer flask. Evaporate the ether from theflask using a steam bath. If any water droplets collect in theflask, add a few millilitres of acetone, and continue toevaporate on the steam bath until a clean, dry residue isobtained
36、. Place the flask in a forced convection drying oven at100 to 105C for 15 to 30 min. Inspect for solvent vapor, ifnone, cool in a desiccator, and weigh (to 0.001 g or 0.0001 g).D1065 96 (2014)128.5 Dissolve the contents of the flask with 50 mL ofisopropyl alcohol conforming to 6.3, add 4 or 5 drops
37、ofthymol blue or phenolphthalein indicator solution, and titratewith the standardized 0.1 N alkali solution in 6.1. When thesolution is too colored to detect with certainty the endpointinternally, titrate until a faint color change is noted. Thenwithdraw approximately 0.5 mL of the solution to a por
38、celainspot plate, and to the portion on the spot plate add 1 drop of theindicator solution. Continue titrating with 0.1-mL incrementsof titrant, followed by testing on the spot plate, until a definitecolor change that persists for at least one minute is obtained.9. Calculation and Report9.1 Calculat
39、e the percentage of unsaponifiable matter in thesample as follows, and report the results to the nearest 0.1 %:Unsaponifiable matter, % 5 A 2 CN 30.302!/B# 3100 (1)where:A = dried residue, g,B = sample used (dry basis), g,C = alkali titrant solution used, mL, andN = normality of the alkali titrant s
40、olution.10. Precision and Bias410.1 PrecisionInterlaboratory Test Program: An inter-laboratory study of the unsaponifiable matter content of threesubstances, tall oil fatty acids, distilled tall oil, and rosin, wererun in 1994. Results for determinations for tall oil fatty acidswere reported for 17
41、laboratories, determinations for distilledtall oil for 16 laboratories and determinations for rosin from 6laboratories. The design of the experiment, similar to that ofPractice E691 and a within-between analysis of the data aregiven in Research Report No. RR:D01-1102.10.2 Test ResultsThe precision i
42、nformation given belowfor the unsaponifiable matter content of naval stores products isfor a comparison of two test results, each of which is theaverage of three test determinations as follows:10.2.1 Repeatability Limit95 % (within labora-tory) = 0.3 %.10.2.2 Reproducibility Limit95 % (between labor
43、a-tory) = 1.1 %.10.3 These terms (repeatability limit and reproducibilitylimit) are used as specified in Practice E177. The respectivestandard deviations among test results, related to the abovenumbers by the factor of 2.8 are as follows:10.3.1 Repeatability standard deviation = 0.1 %.10.3.2 Reprodu
44、cibility standard deviation = 0.4 %.10.4 BiasThis test method has no bias because unsaponi-fiable matter content is defined only in terms of this testmethod.11. Keywords11.1 rosin; tall oil; tall oil fatty acids; unsaponifiable matterASTM International takes no position respecting the validity of an
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47、 comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyr
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