ind Ye ate. rect. Hie, om ion; aq Designation: D 95 - 83 (Reapproved 1990)" 1) Designation MPMS Chapter 10.5, IP® designation 74/82 (88) Standard Test Method for (rere Sd 8 ghwoyirereporaton See TaAGHTO No TSS Water in Petroleum Products and Bituminous Materials by Distillation’ “This standard is ised under the fxd designation D 95; the number immediately flowing the desigeason indicates the yar of crgial adoption or, in the case of revision, the yer of et revision. A number in pzeneses adiats the Year of st eaproval. A Speecdt elon (indicates an editor change sine the last rovson or veaparova, This text method has Been approved by the sponsoring commites and accepted by te cooperating organizations i accordance with established procedures, “This et metho hasbeen approved or se by agencies othe Deparment of Defense an fr isting in the DoD Index of Specifications and Standards ‘ Nore—-Paragaphs 12 and 11.2 were added elton im May 1990 1. Scope 1.1. This test method covers the determination of water in petroleum products, tars, and other bituminous materials by the distillation method. The specific products considered during the development of this test method are listed in Table 1. For bituminous emulsions refer to Test Method D244, This test method, along with ASTM Test Method 14006 (API Chapter 10.2 and IP 358), supersedes the previous edition of ASTM Test Method D 95 (API Standard 2560, 1P 74). [Nore_I—With some types of oil, satsfctory results may be obtained from ASTM Test Method D 4007 (APL Chapter 103, 1P 358, and ASTM Method D 1796 API Chapter 10.6) 1.2 This standiird may involve hazardous materials, oper- ations, and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see 5.1.1.2 and 5.1.1.3, 1.3 The values stated in SI units are to be regarded as the standard. The values in parentheses are for information only. 2. Referenced Documents 2.1 ASTM Standards: D86 Test Method for Distillation of Petroleum Products? D244 Test Methods for Emulsified Asphalts? "This tet method is under the Juratcion of ASTM Commitee D-2 on Pauleum Products and Lubscane apd API Commitee on Pevleum Measure ‘ent ands the zc esponsTbty of Subcommitee 02.02 on Joint ASTMAPI (Commites on Static Perleum Messrement ‘Curent edition approved March 25, 1983, Publsbed January 198, Original pubhet a8 D $5.21, Lat previous eion DS ~ 70 (1880. * dnl Book of ASTM Standard, Vols 05.01 and 05.04, > “ami Book of ASTM Standards, Vol OLDS 1D 1796 Test Method for Water and Sediment in Fuel Oils by the Centrifuge Method (Laboratory Procedure)* 14006 Test Method for Water in Crude Oil by Distillation’ 14007 Test Method for Water and Sediment in Crude Oil by the Centrifuge Method (Laboratory Procedure)® 14057 Practice for Manual Sampling of Petroleum and Petroleum Products? D4177 Method for Automatic Sampling of Petroleum and Petroleum Products? E 123 Specification for Apparatus for Determination of Water by Distillation® 2.2 API Manual of Petroleum Measurements Standards:? Chapter 8.1 Manual Sampling of Petroleum and Peiro- eum Products (ASTM Practice D 4057) Chapter 8.2 Automatic Sampling of Petroleum and Petro- eum Products (ASTM Test Method D 4177) (Chapter 10.2 Determination of Water in Crude Oil by the Distillation Method (ASTM Test Method D 4006) Chapter 10.3 Determination of Water and Sediment in Crude Oil by the Centrifuge Method (Laboratory Proce- dure) (ASTM Test Method D 4007) Chapter 10.6 Determination of Water and Sediment in Fuel Oil by the Centrifuge Method (ASTM Test Method D 1796) 23 British Standard:* 756 Dean and Stark Apparatus 3, Summary of ‘Test Method 3.1 The material to be tested is heated under reflux with a “ Annual Book of ASTM Standards, Vol 05. 5 dnl Book of ASTM Stardards, Vo 05 02. ‘nmal Book of ASTM Standards, Vol 14.02. 7 qvalabe fom American Perleun fst, 120 LSt,N.W, Wasson, be 20005, E avalible fom Anticta Nationa! Standards Insite, 13h, Flor, 11 W. ‘ana Str, New York, NY 10036." ~—>qb > TABLE 1 Type of Solvent-Carrir Liquld Versus Material to be Tested Type ScvenCavargad =Car tobe Tested ‘renste Tapia er, oad ar, wale QBs Ta, 080 far eboc turin, laid asp, tr oo Petleum ciate 15a of, ual, ubrieatng ol, peti Vola spits luoneating grease, ‘watersimmiscible solvent, which co-distills with the water in ‘the sample, Condensed solvent and water are continuously separated in a trap, the water settling in the graduated section of the trap and the solvent returning to the stil. 4, Significance and Use 4.1 A knowledge of the water content of petroleum products is important in the refining, purchase, sale, and transfer of products. 4.2 The amount of water as determined by this method (to the nearest 0,05 volume %) shall be used to correct the volume involved in the custody transfer of oil. >. Solvent-Carrier Liquid 5.1 A solvent-carrier liquid appropriate to the material being tested (see Table 1) shall be used. S.L.1 Aromatic Solvent—The following aromatic solvents, are acceptable: 5.1.1 Industrial Grade Xylene. 5.1.12 A blend of 20 volume % industrial grade toluene and 80 volume % industrial grade xylene (Warning—Flam- mable, Vapor harmful. See Annex Alt.) 5.1.1.3 Petrolewn or-Coal Tar Naphtha (Warning—Ex- tremely fammable. Harmful if inhaled. Vapors may cause fire. See Annex), free of water, yielding not more than 5% distillates at 125°C (257°F) and not less than 20% at 160°C (20°F) when tested by Method D 86 and with a relative density (specific gravity) not lower than 0.8545 at 15.56/ 15.56°C (60/60°F).. 5.1.2 Petroleum Distillate Solvent—A petroleum distillate ecenen-t| H (Grrionaty ? cass On sri’ FIG. 1 Typical Assembly with Glass Stil (Dean and Stark) ea 95 Conapuarion TNTERVAL, wae Tk Foor P FIG. 2 Two-mililitre Receiver Showing Alternative Connections ‘to Glass Stil solvent, 5% boiling between 90° and 100°C (194° and 212°F) and 90% distilling below 210°C (410°F), shall be used. 5.13 Volatile Spirits Solvent—The following volatile spirits solvents are acceptable: 5.1.3.1 Petroleum Spirit, with a boiling range of 100" to 120°C (212° to 248°P) t 5.1.32 Isooctane, of 95% purity or better. 6. Apparatus 6.1 General—The apparatus comprises a glass or metal still, a heater, a reflux condenser, and a graduated glass trap. The stil, trap, and condenser may be connected by any suitable method that produces a leakproof joint. Preferred ‘connections are ground joints for glass and O-rings for metal to glass. Typical assemblies are illustrated in Figs. 1,2, and 3. ‘The stills and traps should be chosen to cover the range of materials and water contents expected. 6.2 Still—A glass or metal vessel with @ short neck and suitable joint for accommodating the reflux tube of the trap shall be used. Vessels of 500, 1000, and 2000-mL nominal capacity have proved satisfactory. el 6.3 Heater—A suitable gas burner or electric heater may be used with the glass stil. A gas ring burner with ports on the inside circumference shall be used with the metal still. ‘The gas ring burner shall be of such dimensions that it may be moved up and down the vessel when testing materials that are likely to form or solidify in the still. 6.4 Glassware—Dimensions and descriptions of typical glassware for use in this method are provided in Specification E123 and British Standard 756. A straight water-cooled condenser with a length of 400 mL is recommended in place of the length of 300 ml specified in British Standard 756. [Nore 2—Instead of standardizing on a particular apparatus specif- cation with respect to dimensions and style, a given apparatus will be domed setisactory when accurate results are obtained by the standard faddition technique described in Section 7. 7, Standardization 7.1 A given assembly of apparatus will be considered sati ad or witif ced 4) p95 ‘convensen——_| ae RECEIVER METAL sTILL— ey ‘SCALE (APPROX) | RING BURNER " Noto—Trap shal be 15 ta 16 mm nine ameter FIG. 3. Typical Assembles with Metal Sti satisfactory when accurate readings are obtained from the addition of known amounts of water from a calibrated buret or pipet to a clear hydrocarbon oil and tested in accordance with Section 9. 7.2 The readings shall be judged accurate if the permis- TABLE 2 Permissible Limite in Miitres Cacaaiy of Vor ot Water Parrisabe Unis for Recolve st Added to ask ecoveced Wator 20° 820°C at 20°C 2 7 T= 005 0 1 1e0% 10 5 2 2 sible limits given in Table 2 for the various sized graduated traps are not exceeded. 7.3 A reading outside the permissible limits suggests a malfunction resulting from vapor leaks, too rapid boiling, inaccuracies in calibration of the trap, or ingress of extra~ neous moisture, Eliminate these factors before repeating the standardization. : 8. Sampling 8.1 Sampling is defined as all steps required to obtain an aliquot of the contents of any pipe, tank, or other system and +o place the sample into the laboratory test container. Only representative samples obtained as specified in Practice 1D 4057 (API Chapter 8.1) and Method D 4177 (APIChapter |ih 095, 8.2) shall be used for this test method. '8.2 The size of the test portion should be based on the expected water content of the sample, such that the water Yield does not exceed the capacity of the trap (unless a trap with a stopcock is used since excess water can be withdrawn into a graduated cylinder). 9. Procedure 9.1 Measure a suitable amount of sample to an accuracy of + 1% and transfer it to the stl 9.2 Measure ordinary liquid samples in a graduated cyl- inder of an appropriate size. Rinse the material adhering to the cylinder with one 50-mL and two 25-mL portions of the Solvent-carrier liquid (see Section 5 and Table 1), Drain the cylinder thoroughly after the sample transfer and each rinsing, 9.3 Weigh solid or viscous materials directly into the stil and add 100 mL of the selected solvent-carrier liquid. In ‘cases of material with a low-water content when large samples must be used, @ solvent-carrier liquid volume in excess of 100 mL may be necessary. ‘9.4 Glass beads or other boiling aids may be added, if necessary, to reduce bumping. ‘9.3 Assemble the components of the apparatus as illus trated in Figs. 1, 2, and 3 choosing the trap in accordance ‘with the expected water content of the sample and making all connections vapor and liquid tight. If a metal still with @ removable cover is used, insert a gasket of heavy paper, moistened with solvent, between the still body and the cover. ‘The condenser tube and trap must be chemically clean to assure free drainage of water into the bottom of the trap. Incest a loose cotton plug in the top of the condenser to prevent condensation of atmospheric moisture inside it Circulate cold water through the jacket of the condenser '9.6 Apply heat to the still, adjusting the rate of boiling so that condensed distillate discharges from the condenser at the rate of 2 to 5 drops per second. If the metal still is used, start beating with the sing burner about 76 mL (3 in.) above TABLE 3 Precision 5 Water Ca pe ee erence, mk Repeating 010 oF {SSO or 2x of the mean, whichever is eater Reprocucany e019 02 S825 02.010 % of tho moan, whichever is eater the bottom of te sill and gradually lower the burner as the distillation proceeds. Continue distillation until no water is Visible in any part ofthe apparatus except in the trap, and the Yolume of water in the trap remains constant for $ min. If there is a persistent ring of water in the condenser tube, carefully increase the rate of distillation or cut off the condenser water fora few minutes. 9.7 When the evolution of water is complete, allow the ‘trap and contents to cool to room temperature. Dislodge any rops of water adhering to the sides of the trap with 2 glass rod or other suitable means and transfer them to the water layer, Read the volume of the water inthe trap to the nearest scale division. 10. Calculation 10.1 Calculate the water in the sample, as weight or volume percent, in accordance with the basis on which the sample was taken, as follows: Water, % = V/A x 100 whe: = volume of water in trap and W'= weight (or volume of sample) Volatile water-soluble material, if present, may be measured as water, 10.2 Report the results as the water content to the nearest 0.05% if the 2-mL receiver has been used and to the nearest, 0.1% if the i0-mL or 25-mL receiver has been used with a 100-mL. or 100-g sample. 11. Precision and Bias f {11 Precision—The criteria described in Section 11.1.1 and { 1.1.2 should be used to judge the acceptability of results (95% probability) when using the 10-mL or 25-ml. traps. ‘The precision when using the 2-mL trap has not been established. : TLL1 Repeatability—The difference between successive test resulis, obtained by the same operator with the same apparatus under constant operating conditions on identical {est material, would, in the long run, in the normal and correct operation of the test method, exceed the values in ‘Table 3 in only one case in twenty. L112 Reproducibiliy—The difference between two single and independent test results obtained by different operators working in different laboratories on identical test material, would, in the long run, in the normal and correct operation of the test method, exceed the values in Table 3 in only one case in twenty. 11.2. Bias—A bias statement is under development, Alah) p95 ANNE: (Mandatory Information) Al. PRECAUTIONARY STATEMENTS ALA Xylene/Toluene Vapors may cause flash fire. ‘Warning—Flammable. Vapor harmful. Keep away from heat, sparks, and open flame. Keep away from heat, sparks, and open flame. Keep container closed, Keep container closed. ‘Use with adequate ventilation, Use with adequate ventilation, Avoid a build-up of vapors and eliminate all sources of Avoid breathing of vapor or spray mist. ignition, especially nonexplosion proof electrical apparatus ‘Avoid prolonged or repeated comtact with skin, and heaters. Avoid prolonged breathing of vapors or spray mist. AL Naphtha Avoid prolonged or repeated skin contact. Warning—Extremely flammable, Harmful if inhaled. ‘Te American Soil or Testing as Matos ck no postion respecting the way any patent righ asserted in connocton with any tern mertaned in he standard. User ofthis standard ar oxeressy advised that determination ofthe vale of any such patert Hh, ae the rk of iningement of Sch ight, aro ently tar own respons. ‘Tl standerd fs aubecto rovson at any the ey te regponibe cna comtes and mus be ovlewed evar ve years and rnot reise, eer racproved or mtvrovt. Your comment rete ear fr auion i standard ofr edaora standares ‘ind snout Ge soorcesed fo ASTM Heacqurtrs, Your conmerts wil scelve carl consideration ate mest ofthe response technical commits, whch you may ated. you feel that your comments have nc eceved fer hearing you shouts mks your Viewa incu tthe ASTI Commitee on Sardar, 1916 Race St, Padi, PA T9103