1、Designation: D 1065 96 (Reapproved 2006)Standard Test Method forUnsaponifiable Matter in Naval Stores, Including Rosin, TallOil, and Related Products1This standard is issued under the fixed designation D 1065; 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of the per-centage of material in Na
3、val Stores products as defined inTerminology D 804 including rosin, tall oil and related prod-ucts, other than insoluble dirt or similar visible foreign matterthat does not yield a water-soluble soap when the sample issaponified with potassium hydroxide.1.2 The values stated in SI units are to be re
4、garded 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-priate safety and health practices and deter
5、mine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 509 Test Methods of Sampling and Grading RosinD 803 Test Methods for Testing Tall OilD 804 Terminology Relating to Naval Stores, Including TallOil and Related ProductsE 177 Practice for Use of
6、 the Terms Precision and Bias inASTM Test MethodsE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Significance and Use3.1 This test method is designed to broaden the scope of theprevious edition of the test method by the inclusion of tall oiland tal
7、l oil derived from products as test materials. TestMethods D 803 currently includes a method for the determi-nation of unsaponifiable matter.3.2 The amount of unsaponifiable matter in tall oil and otherrelated products is important in characterizing such products asit indicates the level of nonacidi
8、c 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. Apparatus4.1 Erlenmeyer or Other Flat-Bottom Flask, of 125-mL to250-mL capacity, with standard-taper 24
9、/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 Cylinder, one of 10 to 25-mL and one of 50to 100-mL capacity.4.5 Beaker, of up to 250-mL capacity.5. R
10、eagents5.1 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 Analytical Reagents of the American Chemical Society,where such specifications are available.3Other gra
11、des may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit use without lessening theaccuracy of the determination.5.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean distilled, or deionizedwater.1This test metho
12、d is under the jurisdiction of ASTM Committee D01 on Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D01.34 on Naval Stores.Current edition approved Nov. 1, 2006. Published November 2006. Originallyapproved in 1949. Last previous edition approve
13、d in 2001 as D 1065 96 (2001).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 Chemicals, American Ch
14、emical 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 National Formulary, U.S.
15、Pharmacopeial Convention, Inc. (USPC), Rockville,MD.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.6. Preparation of Sample6.1 Procurement and handling of samples will vary depend-ing upon the physical state of the material. In all
16、instances, thesampling should conform to accepted sampling techniqueswhich ensure the sample is representative of the material beingsampled.6.2 Uniform liquid material should be mixed well and analiquot removed for analysis. Titer in fatty acid samples shouldbe resolubilized by gentle heating and ag
17、itation. Rosin crystal-lization in liquid samples, such as distilled tall oil (DTO),should be resolubilized by heating to 160C with periodicagitation. Homogeneous representative samples are impera-tive.6.3 Solids that melt at relatively low temperature (that is,tall oil pitch) should be warmed to li
18、quification to facilitatemixing and pouring. Homogeneous representative samples areimperative.6.4 Solids that melt at relatively high temperatures (that is,rosin) should be fractured and chipped if possible, (see TestMethods D 509). The sample taken for analysis shall consist ofsmall pieces of rosin
19、 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 onwhich the test is begun in order to avoid changes in propertiesdue to surface oxidation that is very pronounced on groundrosin having a large
20、 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 form,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
21、solution to 60.001 N using potas-sium acid phthalate, or another accepted primary standard foralkaline titrant, according to accepted quantitative practice.7.2 Ethyl Ether (diethyl ether).7.3 Isopropyl Alcohol (Isopropanol) (91 to 99 %)If notneutral, make neutral to phenolphthalein by adding 0.1 N a
22、lkalisolution dropwise.7.4 Phenolphthalein SolutionDissolve 1.0 g of phenol-phthalein in 100 mL of alcohol conforming to 6.1.7.5 Potassium Hydroxide, Ethanolic (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 %) de
23、natured 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 (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
24、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 the flask, add 30mL water, transfer to a separatory funnel, and rinse the flaskwith an additional 20 mL of water that is added to theseparatory
25、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 stand until the etherlayer separates from the water/soap layer. Drain the aqueoussoap layer (lower layer) into a second separatory funnel,allowing
26、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 layer in the second funnel, add 30mL ether and extract as before. Drain the aqueous soap layerinto the original saponification flask. Add the et
27、her layer fromthe second separatory funnel to the first separatory funnel,thereby combining the extracts. Pour the aqueous soap layerfrom the original saponification 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
28、separatoryfunnel into the original saponification flask again, and add theether layer to the first funnel as before, thereby combining itwith the two previous extracts. Now drain off, and add to thesoap solution already in the original saponification flask, all buta few drops of aqueous soap solutio
29、n 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 drain off all but a few drops, combining it in thesaponification flask.8.3 Again pour the combined aqueous soap layers from theoriginal saponif
30、ication flask into the second separatory funnel,add 30 mL ether, and extract for the fourth time. Afterseparation of the layers, discard the aqueous soap layer (lowerlayer) from the second separatory funnel and add the etherlayer to the combined ether extracts in the first separatoryfunnel. Carefull
31、y 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 water, swirlthe separatory funnel gently, allow the water to settle, and thendrain off and discard the water layer (lower). Repeat thiswashing on
32、ce 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 phenolphthalein solution,and examine for any pink color. If pink color is observed, washonce more with 30-mL water. The absence of pink colorindicates the wa
33、sh 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, rinse the separatory funnel with 15 mL ether and add thisto the tared Erlenmeyer flask. Evaporate the ether from theflask using a steam bath.
34、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. 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, a
35、nd weigh (to 0.001 g or 0.0001 g).8.5 Dissolve the contents of the flask with 50 mL ofisopropyl alcohol conforming to 6.3, add 4 or 5 drops 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 wi
36、th certainty the endpointinternally, titrate until a faint color change is noted. Thenwithdraw approximately 0.5 mL of the solution to a porcelainD 1065 96 (2006)2spot plate, and to the portion on the spot plate add 1 drop of theindicator solution. Continue titrating with 0.1-mL incrementsof titrant
37、, 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 Calculate the percentage of unsaponifiable matter in thesample as follows, and report the results to the nearest 0.1 %:Unsaponifiable matter, % 5 A 2 C
38、N 3 0.302! / B 3 100 (1)where:A = dried residue, g,B = sample used (dry basis), g,C = alkali titrant solution used, mL, andN = normality of the alkali titrant solution.10. Precision and Bias410.1 PrecisionInterlaboratory Test Program: An inter-laboratory study of the unsaponifiable matter content of
39、 threesubstances, tall oil fatty acids, distilled tall oil, and rosin, wererun in 1994. Results for determinations for tall oil fatty acidswere reported for 17 laboratories, determinations for distilledtall oil for 16 laboratories and determinations for rosin from 6laboratories. The design of the ex
40、periment, similar to that ofPractice E 691 and a within-between analysis of the data aregiven in Research Report No. D01-1102.10.2 Test ResultsThe precision information given belowfor the unsaponifiable matter content of naval stores products isfor a comparison of two test results, each of which is
41、theaverage of three test determinations as follows:10.2.1 Repeatability Limit, 95 % (within labora-tory) = 0.3 %.10.2.2 Reproducibility Limit, 95 % (between labora-tory) = 1.1 %.10.3 These terms (repeatability limit and reproducibilitylimit) are used as specified in Practice E 177. The respectivesta
42、ndard 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 Reproducibility standard deviation = 0.4 %.10.4 BiasThis test method has no bias because unsaponi-fiable matter content is defined only in terms
43、 of this testmethod.11. Keywords11.1 rosin; tall oil; tall oil fatty acids; unsaponifiable matterASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determi
44、nation of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or wi
45、thdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that y
46、our 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 copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (si
47、ngle or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).4Supporting data are available from ASTM International Headquarters. RequestRR:D01-1102.D 1065 96 (2006)3
