Designation: D 95 – 99
An American National Standard
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American Association State Highway Transportation Standard AASHTO No. T55
Designation: Manual of Petroleum Measurement Standards (MPMS), Chapter 10.5 Designation: 74/82 (88)
Standard Test Method for
Water in Petroleum Products and Bituminous Materials by Distillation1 This standard is issued under the fixed designation D 95; the number immediately following the designation indicates the year of original adoption adopt ion or, in the case of revisio revision, n, the year of last revision. revision. A numb number er in parentheses indicates indicates the year of last reapproval. reapproval. A supersc superscript ript epsilon (e) indicates an editorial change since the last revision or reapproval. This standard has been approved for use by agencies of the Department of Defense.
e1 NOTE—Footnote 1 and the Referenced Documents were corrected editorially to comply with the ASTM-API joint standard contract in October 2002. Warning notes were editorially moved into the standard text in October 2002.
1. Sco Scope pe
D 1796 Test Method for Water Water and Sediment in Fuel Oils by the Cent Centrifu rifuge ge Meth Method od (Lab (Laborat oratory ory Proc Procedur edure) e) (API 3 MPMS Chapter 10.6) D 4006 Test Method for Water Water in Crude Oil by Distillation (API MPMS Chapter 10.2)4 D 4057 4057 Pra Practi ctice ce for Man Manual ual Sam Sampli pling ng of Pet Petrol roleum eum and 4 Petroleum Products (API MPMS Chapter 8.1) D 4177 Prac Practice tice for Automatic Automatic Sampling Sampling of Petr Petroleum oleum and 4 Petroleum Products (API MPMS Chapter 8.2) D 58 5854 54 Pract Practic icee fo forr Mi Mixi xing ng an and d Ha Hand ndli ling ng of Li Liqu quid id Sample Sam pless of Pet Petrol roleum eum and Pet Petrol roleum eum Pro Produc ducts ts (API MPMS Chapter 8.3)5 E 123 Specifica Specificatio tion n for App Appara aratus tus for Det Determ ermina inatio tion n of Water by Distillation 6 Standards:7 2.2 API Standards: MPMS Chapter Chapter 8.1 Man Manual ual Sam Sampli pling ng of Pet Petrol roleum eum and Petroleum Products (ASTM Practice D 4057) MPMS Chapter Chapter 8.2 Autom Automatic atic Sampling Sampling of Petr Petroleum oleum and Petroleum Products (ASTM Practice D 4177) MPMS Chapter Chapter 8.3 Mixing and Handling Handling of Liquid Samples Samples of Petro Petroleum leum and Petro Petroleum leum Products (ASTM Pract Practice ice D 5854) MPMS Chapter Chapter 10.2 Deter Determina mination tion of Water Water in Crude Oil by the Distillation Method (ASTM Test Method D 4006) MPMS Chapter Chapter 10.6 Te Test st Method for Water Water and Sediment in
1.1 This test method covers covers the deter determina mination tion of water in the range from 0 to 25 % volume in petroleum products, tars, and other bituminous materials by the distillation method. NOTE 1—Volatile water-soluble material, if present, may be measured as water.
1.2 The specific products considered considered during the development of this test method are listed in Table Table 1. For bitum bituminous inous emulsions refer to Test Method D 244. For crude oils, refer to Test Method D 4006 (API MPMS Chapter 10.2). NOTE 2—With some types of oil, satisfactory results may be obtained from Test Method D 1796 (API MPMS Chapter 10.6).
1.3 The values values stated stated in SI units are to be reg regard arded ed as the standard. The values in parentheses are for information only. standa ndard rd does not purport purport to add addre ress ss all of the 1.4 This sta safe sa fety ty co conc ncer erns ns,, if an anyy, as asso soci ciat ated ed wi with th it itss us use. e. It is th thee responsibility of the user of this standard to establish appro priate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see Section 5. 2. Referenced Documents 2.1 ASTM Standards: D 244 Test Methods for Emuls Emulsified ified Asphalts Asphalts2 1
Thiss test method Thi method is und under er the jurisdicti jurisdiction on of ASTM Committee Committee D02 on Petroleum Products and Lubricants and the API Committee on Petroleum Measurement, and is the direct responsibility of Subcommittee D02.02/COMQ, the joint ASTM-API ASTM-A PI Commit Committee tee on Static Petrole Petroleum um Measurem Measurement. ent. Currentt edition approved Curren approved June 10, 1999 1999.. Publi Published shed August 1999. Originally published publis hed as D 95–21. 95–21. Last previous edition D 95–8 95–83 3 (1990 (1990). ). 2 Vol 04.03. Annual Book of ASTM Standard Standards, s, Vol
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Annual Book of ASTM Standards Standards,, Vol 05.01. Annual Book of ASTM Standards Standards,, Vol 05.02. 5 Annual Book of ASTM Standards Standards,, Vol 05.03. 6 Annual Book of ASTM Standards Standards,, Vol 14.02. 7 Published as Manual of Petroleum Measurement Standards. Available from the American Petroleum Institute (API), 1220 L St., NW, Washington, DC 20005. 4
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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D 95 – 99
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3.1 The material material to be tested is heated under reflux reflux with a water-immiscible solvent, which co-distills with the water in the samp sample. le. Conde Condensed nsed solvent and water are cont continuou inuously sly separated in a trap, the water settling in the graduated section of the trap and the solvent returning to the still.
5.1.3.2 Iso-octane, of 95 95% % pu puri rity ty or be bett tter er.. (Warning— Extremely flammable. Harmful if inhaled. Vapors may cause fire.) 5.2 Solvent Blank —The —The water content of the solvent shall be determined by distilling an equivalent amount of the same solvent used for the test sample in the distillation apparatus and testing as outlined in Section 9. The blank shall be determined to the nearest scale division and used to correct the volume of water in the trap in Section 10.
4. Signi Significanc ficancee and Use
6. Appa Apparatus ratus
4.1 A knowl knowledge edge of the water content content of petroleum petroleum products products is imp import ortant ant in the refi refinin ning, g, pur purcha chase, se, sal sale, e, and tra transf nsfer er of products. 4.2 The amount of water as determined determined by this test method (to the nea neares restt 0.0 0.05 5 vol volume ume %) may be use used d to cor correc rectt the volume involved in the custody transfer of petroleum products and bituminous materials. 4.3 The all allowa owable ble amount amount of wat water er may be spe specifi cified ed in contracts.
6.1 General—Th —Thee app appara aratus tus com compri prises ses a gla glass ss or met metal al still, a heater, a reflux condenser, and a graduated glass trap. The still, trap, and condenser may be connected by any suitable method that produces a leakproof joint. Preferred connections are ground ground joi joints nts for gla glass ss and O-rings O-rings for metal metal to gla glass. ss. Typical assemblies are illustrated in Fig. 1, Fig. 2, and Fig. 3. The stills and traps should be chosen to cover the range of materi mat erials als and wat water er con conten tents ts exp expect ected. ed. On ass assemb embly ly,, car caree should be taken to prevent the joints from freezing or sticking. This may be prevented by the application of a very thin film of stopcock grease. 6.2 Still—A glass or metal vessel with a short neck and suitable joint for accommodating the reflux tube of the trap shall sha ll be use used. d. Vess essels els of 500 500,, 100 1000, 0, and 200 2000-m 0-mL L nom nomina inall capacity have proved satisfactory. 6.3 Heater —A —A suitable gas burner or electric heater may be used with the glass still. 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 foam or solidify in the still. 6.4 Glassware—Di —Dimen mensio sions ns and des descri cripti ptions ons of typ typica icall glassware for use in this test method are provided in Specification E 123.
Fuel Oils by the Centrifuge Method (Laboratory Procedure) (ASTM Test Method D 1796) 3. Summa Summary ry of Test Method
5. Solvent-Carrier Liquid 5.1 A solvent-carrie solvent-carrierr liquid appropriate appropriate to the material being tested (see Table 1) shall be used. 5.1.1 Aromatic —The foll following owing arom aromatic atic solv solvents ents Aromatic Solvent —The are acceptable: Industrial Grade Xyle Xylene ne—( Warning—Flammable. 5.1.1.1 Industrial —(Warning— Flammable. Vapor harmful.) 5.1.1.2 A blen blend d of 20 volume % industrial industrial grade grade toluene toluene and 80 volume % industrial grade xylene. ( Warning— Flammable. Warning—Flammable. Vapor harmful.) 5.1.1.3 Petr free ee of wa wate terr, Petrole oleum um or Coa Coall Tar Nap Naphth htha a, fr yielding not more than 5% distillates at 125°C (257°F) and not less than 20% at 160°C (320°F) and with a relative density (speci (sp ecific fic gra gravit vity) y) not low lower er tha than n 0.8 0.8545 545 at 15. 15.56/ 56/15. 15.56° 56°C C Warning—Extr (60/60°F) (60/6 0°F).. (Warning— Extremel emely y flamm flammable. able. Harmful if inhaled. Vapors may cause fire.) Petroleum Distillate Solvent —A 5.1.2 Petroleum —A petroleum distillate solvent, 5% boiling between 90 and 100°C (194 and 212°F) and 90% distilling below 210°C (410°F), shall be used. Percent may be determined by mass or by volume. These solvents are available from most chemical companies under the name of Warning—Flammable. stoddard stodd ard solvent or ligr ligroine. oine. ( Warning— Flammable. Vapor harmful.) 5.1.3 Volatile Spirits Solvent —The —The following volatile spirits solvents are acceptable: 5.1.3.1 Petroleum Spirit , with a boiling range from 100 to 120°C (212 to 248°F). (Warning— ( Warning—Flammable. Flammable. Vapor harmful.)
NOTE 3—Instead of standardizing on a particular apparatus specification with respect respect to dim dimensi ensions ons and styl style, e, a give given n app appara aratus tus will be deemed satisfactory when accurate results are obtained by the standard
TABLE 1 Type of Solvent-Carrier Liquid Versus Versus Material to Be Tested Typ ype e of So Solv lven entt-Ca Carr rrie ierr Li Liqu quid id Aro roma mati tic c
Petrol Pet roleum eum dis distil tillat late e Vol olat atiile spi piri rits ts
Mate Ma teri rial al to be Tes este ted d aspha asp halt lt,, ta tarr, co coa al ta tarr, wate terr gas ta tarr, ro road ad tar, cut-back bitumin, liquid asphalt, tar acid road roa d oil oil,, fue fuell oil oil,, lub lubric ricati ating ng oil oil,, pet petrol roleum eum sulfonates lubr lu briica cati tin ng gr gre eas ase e
FIG. 1 Typical Assembly with Glass Still
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D 95 – 99
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FIG. 2 Two-millilitre Receiver Showing Alternative Connections to Glass Still
8.1.2 In styles E and F, as specified specified in Table 2, each major subdivision (0.1 mL, 1.0 mL, 2.0 mL, 4.0 mL, and 5.0 mL in the case of Style E; 0.05 mL, 0.5 mL, 1.0 mL, 1.5 mL, and 2.0 mL in the case of Style F) shall be verified. 8.2 The entire glassware glassware assembly assembly shall be cali calibrat brated ed prior to use as follows. 8.2.1 Put 400 mL of dry (0.02 % water water maximum) xylene xylene or the solvent to be utilized in the analysis of unknown samples into the apparatus and test in accordance with Section 9. When complete, discard the contents of the trap and add the volume of water as specified as first test in Table 3 directly to the distillation flask and test in accordance with Section 9. 8.2.2 Repea Repeatt the test in 8.2.1, and add the volume volume specified specified as second test in Table 3 directly to the flask. The assembly of the apparatus is satisfactory only if the trap readings are within the tolerances specified in Table 3. 8.3 A rea readin ding g out outsid sidee the per permis missib sible le lim limit itss sug sugges gests ts a malfun mal functi ction on res result ulting ing fro from m vap vapor or lea leaks, ks, too rap rapid id boi boilin ling, g, inaccuracies in calibration of the trap, or ingress of extraneous moisture. Eliminate these factors before repeating the standardization.
addition technique described in Section 8.
9. Proc Procedur eduree
7. Sampl Sampling ing
Caution: The precision of this test method will be affected by NOTE 4— 4—Caution: water droplets adhering to surfaces in the apparatus and therefore not settling into the water trap to be measured. To minimize the problem, all apparatus must be cleaned chemically at least daily to remove surface films and debris, which hinder free drainage of water in the test apparatus. apparatus. More frequent cleaning is recommended if the nature of samples being run causes persistent contamination.
7.1 Sam Sampli pling ng is defi defined ned as all steps steps req requir uired ed to obt obtain ain an aliquot of the contents of any pipe, tank, or other system and to place pla ce the sam sample ple int into o the lab labora orator tory y tes testt con contai tainer ner.. Onl Only y repres rep resent entati ative ve sam sample pless obt obtain ained ed as spe specifi cified ed in Pra Practi ctices ces D 4057 4057 (AP (APII MPMS Chapter Chapter 8.1) and D 4177 4177 (AP (APII MPMS Chapter 8.2) shall be used for this test method. 7.2 7. 2 Th Thee si size ze of th thee te test st po port rtio ion n sh shou ould ld be ba base sed d on th thee 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 permitting excess water to be withdrawn into a graduated cylinder). 7.3 Pra Practi ctice ce D 585 5854 4 (AP (APII MPMS Chapter Chapter 8.3) conta contains ins informati infor mation on on samp sampling ling and homo homogeniz genization ation ef effficie iciency ncy of unknow unk nown n mix mixers ers.. Thi Thiss tes testt met method hod sho should uld not be fol follow lowed ed withou wit houtt str strict ict adh adhere erence nce to Pra Practi ctice ce D 585 5854 4 (AP (APII MPMS Chapter 8.3).
9.1 Measu Measure re a suit suitable able amount amount of sample to an accur accuracy acy of 6 1% and transfer it to the still. 9.2 Measure ordinary liquid liquid samples in a graduated cylinder cylinder of an app approp ropria riate te siz size. e. Rin Rinse se the mat materi erial al adh adheri ering ng to the cylind cyl inder er wit with h one 5050-mL mL and two 25-mL portion portionss 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 visco viscous us mate materials rials directly directly into the still 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, a solvent-carrier liquid volume in excess of 100 mL may be necessary. 9.4 9. 4 Gl Glas asss be bead adss or ot othe herr bo boil ilin ing g ai aids ds ma may y be ad adde ded, d, if necessary, to reduce bumping. 9.5 Ass Assem emble ble the com compon ponent entss of the app appara aratus tus,, as ill illusustrat tr ated ed in Fi Fig. g. 1, Fi Fig. g. 2, an and d Fi Fig. g. 3, ch choo oosi sing ng th thee tr trap ap in accordance with the expected water content of the sample and making all connections vapor and liquid tight. If a metal still with a removable cover is used, insert a gasket of heavy paper, moistened with solvent, between the still body and the cover. The con conden denser ser tube and tra trap p mus mustt be che chemic micall ally y cle clean an to ensure free drainage of water into the bottom of the trap. Insert a loo loose se cot cotton ton plug in the top of the condens condenser er to pre preven ventt condensation of atmospheric moisture inside it. Circulate cold water through the jacket of the condenser. 9.6 Apply heat to the still, adjusting adjusting the rate of boili boiling ng so that condensed distillate discharges from the condenser at the rate of two to five drops per second. If the metal still is used, start heating with the ring burner about 76 mm (3 in.) above the
8. Standardization 8.1 The accuracy accuracy of the gradu graduatio ation n marks on the trap shall be cert certified ified or veri verified, fied, using only national national or inte internati rnational onal standards, such as National Institute of Standards and Technology (NIST)8 traceable equipment. Verification shall be with a traceable 5 mL Micro Burette or Micro Pipette, readable to the nearest 0.01 mL. 8.1.1 8. 1.1 In st styl yles es A, B, C, an and d D, as sp spec ecifi ified ed in Tabl Tablee 2 (Table 1 in Specification E 123), each subdivision (that is, 0.1 mL through 1.0 mL) in the conical portion of the tube shall be verified. Thereafter, each major subdivision (that is, 2.0 mL, 3.0 mL, 4.0 mL, and up to the total volume of the trap) shall be verified.
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National Nation al Institu Institute te of Stand Standards ards and Technology Technology,, U.S. Department of Commerce, Gaithersburg, MD 20899.
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D 95 – 99
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NOTE 1—Trap shall be 15 to 16 mm in inside diameter FIG. 3 Typical Assemblies with Metal Still TABLE TA BLE 2 Spec Specificati ifications ons and Sizes of Traps Description
Style
Top of Graduated Tube
Bottom of Graduated Tube
Bottom of Vapor Tube
Size of Trap mL
Range mL
Smallest Scale Division, mL
Scale Error Maximum, mL
A
ST Joint
Conical
ST Joint
10
B C D E
ST ST ST ST
Joint Joint Joint Joint
Conical Conical Conical Round
ST Joint Plain Plain ST Joint
F
ST Joint
Round
ST Joint
25 25 25 5 10 2
0 t o 1 .0 >1.0 to 10.0 0 t o 1 .0 > 1 .0 to 2 5 1 .0 to 2 5 0 to 5 .0 0 to 10.0 0 to 2 .0
0 .1 0 .2 0 .1 0 .2 0 .2 0 .1 0 .1 0 .0 5
0.05 0.1 0.05 0.1 0 .1 0.05 0 .1 0.025
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D 95 – 99 TABLE TA BLE 3 Perm Permissibl issible e Limits in Millilit Milliliters ers Capacity of Receiver at 20°C 20°C
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11. Repor Reportt
Volume of Water Added to Flask at 20°C
Permissible Limits for Recovered Water at 20°C
11.1 Repor 11.1 Reportt the resul results ts as the water content content to the nearest nearest 0.05% if the 2-mL receiver has been used and to the nearest 0.1% if the 10-mL or 25-mL receiver has been used with a 100-mL or 100-g sample.
Round trap 2 2
1st Test 2nd Test
1 1.9
1 6 0.05 1.9 6 0.05
5 5
1st Test 2nd Test
1 4.5
1 6 0.05 4.5 6 0.05
10 10
1st Test 2nd Test
5 9
5 6 0.1 9 6 0.1
Conical trap 10 10
12.1 Precision—The criteria described in 12.1.1 and 12.1.2 should be use should used d to jud judge ge the acc accept eptabi abilit lity y of res result ultss (95 (95% % probability) when using the 10 or 25-mL traps. The precision when using the 2-mL trap has not been established.
1st Test 2nd Test
1 9
1 6 0.1 9 6 0.2
NOTE 5—Practice D 6300 was not used in obtaining precision data.
25 25
1st Test 2nd Test
12 24
12 6 0.2 24 6 0.2
12. Prec Precisio ision n and Bias
12.1.1 Repeatability—The dif differe ference nce betwe between en succe successiv ssivee test res test result ults, s, obt obtain ained ed by the sam samee ope operat rator or wit with h the sam samee apparatus under constant operating conditions on identical test materi mat erial, al, would, would, in the long run run,, in the normal normal and cor correc rectt operation of the test method, exceed the values in Table 4 in only one case in twenty. 12.1.2 Reproducibility —The difference between two single and inde independe pendent nt test results obtai obtained ned by dif differe ferent nt opera operators tors working worki ng in dif differe ferent nt labo laborator ratories ies on iden identical tical test mate material rial,, would, in the long run, in the normal and correct operation of the test method, exceed the values in Table 4 in only one case in twenty. 12.2 Bias—A —Ass th ther eree is no ac acce cept pted ed re refe fere renc ncee ma mate teri rial al suitable for determining bias for the procedure described in this test method for meas measurin uring g wate waterr in petr petroleum oleum products products and bituminous materials by distillation, no statement about bias is made.
bottom of the still bottom still and graduall gradually y low lower er the burner burner as the distillat disti llation ion proce proceeds. eds. Conti Continue nue dist distilla illation tion unti untill no water is visible in any part of the apparatus except in the trap and the volume of water in the trap remains constant for 5 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 for a few minutes. 9.7 When the evolution evolution of water is complete, complete, allow the trap and contents to cool to room temperature temperature.. Dislo Dislodge dge any drops of wa wate terr ad adhe heri ring ng to th thee si side dess of the tr trap ap wi with th a gl glas asss or polytetrafluoroethylene (PTFE) rod or other suitable means and transfer them to the water layer. Read the volume of the water in the trap to the nearest scale division. 9.8 A solvent solvent blank shall be established, established, as outlined in 5.2.
13. Keyw Keywords ords
10. Calc Calculati ulation on
13.1 bituminous materials; materials; distillation; petroleum products; products; solvent carrier liquid; water by distillation; water content
10.1 Calculate the water water in the sample, sample, as weight or volume percent, in accordance with the basis on which the sample was taken, as follows: 10.1.1 Water ater,, % (V/V) =
TABLE TAB LE 4 Precision
~Volume in water trap, mL! 2 ~Water in solvent blank, mL! 3 100 Volume in test sample, mL
Type
(1)
Repeatability
0.0–1.0 1.1– 1. 1–25 25
Reproducibility
0.0–1.0 1.1– 1. 1–25 25
10.1.2 Water ater,, % (V/m (V/m)) = ~Volume of water in trap, mL! 2 ~Water in solvent blank, mL! 3 100 Mass of test sample, g (2)
Water Collected, mL
Difference, mL 0 .1 0.1 0. 1 or or 2 % of of the the me mean an,, whi which chev ever er is greater 0 .2 0.2 0. 2 or or 10 10 % of of the the me mean an,, whi which chev ever er is greater
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