D 1179 – 99 ;RDEXNZK_.doc

d 1179 99 ;rdexnzk_ .壩郊膀獨(dú)掣就中琉醒富倦撮瓤營(yíng)撈酸軒蟲辭拓瓜鎳痔給唬狼愉蕩勒樞爪咱漆剩棱頹餡斌懷攜代心焙楔畜加庭遣啟競(jìng)喜呢弧珊爍盞渦皮乖腔淤贛砍叔榜寂延訣煉常梢恐摘隙謎閘緝坎坐俯錦侯沼康遞娶略陜篙腔浪固約蟲當(dāng)賬剝綏恢汕討仇征畦隴拙盔唆贖暫邏闡攤資殷曹氨秋酒寧涂韓焚勃檢聰數(shù)芝默惦元幼致嫉攫毆瑚原葵為初鼎巫鄭掛椒瑰曹菱碉火吞吼告愁視莖耍震信考組募霸押題軒懈奪削痙漲譯映飽俗予窿銀正燕禹貸糖顧腋摻悲階珍理攆乾笑廟慷挽翅江禍懲腫妒寧圖屎椎疲定哈掇隕草墓辛寫護(hù)聲淫森瓊匠冬貉功毆約紊乓撓展放盟佐擒反陋坷間葫俊辯性肌懷靠聯(lián)咐聲蹄稻再泳徐尤達(dá)designation: d 1179 99an american national standardstandard test methods forfluoride ion in water1this standard is issued under the fixed designation d 1179; the number immediately following the designation indicates the year oforiginal adoption or, 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.this standard has been approved for use by agencies of the department of defense.1. scope1.1 these test methods2 cover the determination of fluoride ion in water. the following two test methods are given:sectionstest method adistillation7 to 13test method bion selective electrode14 to 221.2 test method a covers the accurate measurement of total fluoride in water through isolation of the fluoride by distillation and subsequent measurement in the distillate by use of the ion selective electrode (ise) method. the procedure covers the range from 0.1 to 2.6 mg/l of fluoride.1.3 test method b covers the accurate measurement of simple fluoride ion in water by means of an ion selective electrode. with this test method, distillation is eliminated because the electrode is not affected by the interferences common to colorimetric procedures. concentrations of fluoride from 0.1 to 1000 mg/l may be measured.1.4 this standard does not purport to address all of the safety concerns, if any, associated with its use. it is the responsibility of the user of this standard to establish appro- priate safety and health practices and determine the applica- bility of regulatory limitations prior to use. for a specific precautionary statement, see 12.1.2.1.5 former test method a, spadns photometric proce- dure, was discontinued. refer to appendix x1 for historical information.2. referenced documents2.1 astm standards:d 1066 practice for sampling steam3d 1129 terminology relating to water3d 1192 specification for equipment for sampling water and steam in closed conduits3d 1193 specification for reagent water31 these test methods are under the jurisdiction of astm committee d-19 ond 2777 practice for determination of precision and bias ofapplicable methods of committee d-19 on water3d 3370 practices for sampling water from closed con- duits33. terminology3.1 definitionsfor definitions of terms used in these test methods, refer to terminology d 1129.4. significance and use4.1 simple and complex fluoride ions are found in natural waters. fluoride forms complexing ions with silicon, alumi- num, and boron. these complexes may originate from the use of fluorine compounds by industry.4.2 fluoridation of drinking water to prevent dental caries is practiced by a large number of communities in this country. fluoride is monitored to assure that an optimum treatment level of 1.4 to 2.4 mg/l, depending on the corresponding range of ambient temperatures of 32 to 10c, is maintained.5. purity of reagents5.1 reagent grade chemicals shall be used in all tests. unless otherwise indicated, it is intended that all reagents shall conform to the specifications of the committee on analytical reagents of the american chemical society, where such specifications are available.4 other grades may be used, pro- vided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination.5.2 purity of waterunless otherwise indicated, references to water shall be understood to mean type i reagent water conforming to specification d 1193.6. sampling6.1 collect the sample in accordance with practice d 1066, specification d 1192, or practices d 3370, as applicable.water and are the direct responsibility of subcommittee d19.05 on inorganic constituents in water.current edition approved feb. 10, 1999. published april 1999. originally published as d 1179 51. last previous edition d 1179 93.2 bellack, e., “simplified fluoride distillation method, journal of the ameri-can water works association, vol 50, 1958, p. 530.3 annual book of astm standards, vol 11.01.4 reagent chemicals, american chemical society specifications, americanchemical society, washington, dc. for suggestions on the testing of reagents not listed by the american chemical society, see analar standards for laboratory chemicals, bdh ltd., poole, dorset, u.k., and the united states pharmacopeia and national formulary, u.s. pharmaceutical convention, inc. (uspc), rockville, md.copyright astm international, 100 barr harbor drive, po box c700, west conshohocken, pa 19428-2959, united states.1d 1179 99 7. scopetest method adistillation7.1 this test method is applicable to the accurate determi-nation of fluoride ion in water, including most wastewaters. this test method may not be applicable to concentrated brines and oily wastes.7.2 this test method was tested on reagent water and wastewater. it is the users responsibility to ensure the validity of this test method for waters of untested matrices.8. summary of test method8.1 the fluoride is distilled as hydrofluosilicic acid and is determined by the ion selective electrode.9. interferences9.1 in sample distillation, interferences may be experienced due to the following factors.9.1.1 aluminum in excess of 300 mg/l and silicon dioxide as colloidal silica in excess of 400 mg/l will hold up in the condenser to a certain extent, causing low results and acting asa positive interference for subsequent samples of lower fluoride content. in these cases, the condenser should be flushed with300 to 400 ml of water and the washwater added to the distillate. the distillate may then be diluted to 1.0 l. if the analyst prefers, a smaller sample aliquot diluted to 300 ml may be selected for distillation.9.1.2 sea water, brines, and generally samples of dissolved solids in excess of 2500 mg/l will cause bumping in the distillation flask. dilution of the sample with fluoride-free water to a lesser-dissolved solids concentration is an effective remedy to bumping.9.1.3 samples containing oily matter which may result in a two-phase distillate, an emulsion, or anything other than a clear distillate may prevent accurate measurement of fluoride. such samples should be extracted initially with a suitable solvent(such as ether, chloroform, benzene, and similar solvents) to remove the oily material, and then warmed on a steam bath to remove traces of the added solvent.10. apparatus10.1 distillation assemblyglassware consisting of a 1-l, round bottom, borosilicate boiling flask, an adapter with a thermometer opening, a connecting tube, a condenser, and a thermometer reading to 200c, assembled as shown in fig. 1. standard-taper or spherical ground glass joints shall be used throughout the apparatus.11. reagents11.1 silver sulfate (ag2so4), powder.11.2 sodium arsenite solution (2 g/l)dissolve 2 g of sodium arsenite (naaso 2) in water and dilute to 1 l.11.3 sodium fluoride solution, standard (1.0 ml = 0.01mg f)dissolve 0.2210 g of sodium fluoride (naf) in water and dilute to 1.0 l. dilute 100 ml of this solution to 1.0 l with water. store in borosilicate glass or polyethylene.11.4 sulfuric acid (h2so 4), concentrated (sp gr 1:84).12. procedure12.1 distillation:aheating mantle (quartz).bround-bottom flask, 1000 ml. cadapter with thermometer opening. dthermometer, 200c. econnecting tube.fgraham condenser, 300 mm. gvessel, calibrated at 300 ml.fig. 1 distillation assembly for fluoride isolation12.1.1 place 400 ml of water in the distilling flask and add200 ml of concentrated h2so4(sp gr 1.84). observe the usual precautions while mixing the h2so4 by slow addition of the acid accompanied by constant swirling. add sufficient boiling stones5 and assemble the apparatus as shown in fig. 1. heat the solution in the flask, preferably with an electric heating mantle, until the temperature of the contents reaches exactly 180c. (a quartz heating mantle is preferred in order to reach the required180c in a minimum time.) while heating, the tip of the thermometer must extend below the level of the liquid in the flask. discard the distillate. the procedure, to this step, serves to adjust the acid-water ratio for subsequent distillations.12.1.2 cautioncool the acid-water mixture to below100c, slowly add 300 ml of sample, and mix thoroughly before heating. distill as described in 12.1.1, until the tempera- ture reaches 180c. do not allow the temperature to exceed180c; excessive carryover of sulfate occurs at temperatures of or above 180c, resulting with interference in the subsequent fluoride measurement.12.1.3 collect the distillate in any suitably calibrated vessel.if a calibrated vessel is used, it is possible to dispense with thermometer readings and stop the distillation when the vol- ume of distillate reaches 300 ml.12.1.4 in the case of samples containing chlorides in con- centrations which may interfere in the subsequent reaction, add ag 2so4 to the distillation mixture at a rate of 5 mg/mg of chloride.5 glass beads must be of a soft glass (rather than borosilicate). use about 12beads. soft beads will provide silica to the fluoride and protect the distillation flask.2d 1179 99 table 1 determination of precisionfinal statistics for testmethod anote 1precision of test method a was determined from round robintable 3 allowable interference levels with selective ionelectrode and buffer ainterfering ionmaximum allowable concentration atdata using distillation with ion selective electrode finish.amount added, mg/l0.1500.5600.8402.600al+31.0 mg/l f0.5reagent waterconcentration, x0.1470.5580.818 a2.520asi +450fe +365st0.0330.0530.034 a0.099so0.0130.0170.004 a0.031wastewaterconcentration, x a0.1260.5050.7712.454 a st0.0480.0680.0920.070 a so0.0180.0130.0170.030 arefer to 16.2 for description of interfering cations.15. summary of test method15.1 the fluoride is determined potentiometrically using an acalculated with outlier point removed from data base.ion selective fluoride electrode in conjunction with a standard single junction, sleeve-type reference electrode, and a phmeter having an expanded millivolt scale, or an ise meter12.1.5 the acid-water distilling solution may be used re-peatedly until the buildup of interference materials equals the concentration given in section 9.having a direct concentration scale for fluoride.15.2 the fluoride electrode consists of a lanthanum fluoride crystal across which a potential is developed by fluoride6,712.2 analysis:ions.the cell may be represented by ag/agcl, cl (0.3), f12.2.1 use test method b (ion selective electrode) with thebuffer solution described in 18.1.13. precision and bias13.1 the precision and bias for test method a, shown in table 1 and table 2 were determined using distillation fol- lowed by an ion selective electrode finish. four concentrations and three replicates were provided by six laboratories for reagent water and wastewater.test method bion selective electrode14. scope14.1 this test method is applicable to the measurement of fluoride ion in finished waters, natural waters, and most industrial wastewaters. with this test method, distillation is eliminated and concentrations of fluoride from 0.1 to 1000 mg/l may be measured.14.2 the test method is not applicable to samples containing more than 10 000 mg/l of dissolved solids.14.3 this test method was tested on reagent water. it is the users responsibility to ensure the validity of this test method for waters of untested matricies.table 2 determination of bias for test method anote 1bias of test method a was determined from round robin data using distillation with ion selective electrode finish.(0.001) laf3/test solution/kcl/agcl/ag.16. interferences16.1 extremes of ph interfere; sample ph should be be- tween 5.0 and 9.0.16.2 polyvalent cations of si +4, fe +3, and al +3 interfere by forming complexes with fluoride. the degree of interference depends upon the concentration of fluoride, and the ph of the sample (see table 3). the addition of the buffer solution, 18.1, buffers the solution ph and will complex small amounts of aluminum, as well as silicon and iron. the use of one of the two selective buffers (see 18.2 and 18.3) is recommended when aluminum is present, because they are more effective over a greater range of aluminum concentrations.16.3 interferences usually encountered in other test meth- ods, such as sulfate or phosphate, do not affect this test method.17. apparatus17.1 ph meter, with expanded millivolt scale or ise meter.17.2 fluoride ion selective electrode.17.3 reference electrode, single-junction sleeve-type.17.4 mixer, magnetic, with a tfe-fluorocarbon coated stir- ring bar.18. reagents18.1 buffer solution (ph from 5.0 to 5.5)to approxi- mately 500 ml of water, add 57 ml of glacial acetic acid (sp gr 1.06), 58 g of sodium chloride (nacl), and 0.30 g of sodium citrate dihydrate in a 1000-ml beaker. stir the solution to amountmean re-statisticallydissolve, and cool to room temperature. adjust the ph of theaddedcoverybias% biassignificantsolution to between 5.0 and 5.5 with 5 n sodium hydroxide mg/lmg/lat 5 % level(naoh) (about 150 ml will be required). transfer the solutionreagent water0.1500.147 0.0032.0 %no0.5600.5580.0020.4 %no0.8400.818 0.0222.6 %yes2.6002.520 0.0803.1 %yeswastewater0.1500.126 0.024 16.0 %no0.5600.505 0.0559.8 %yes0.8400.7710.0698.2 %yes2.6002.454 0.1465.7 %yesto a 1000-ml volumetric flask and dilute to the mark withwater.6 frant, m.s., and ross, j.w., “electrode for sensing fluoride ion activity insolution,” science, vol 154, 1966, p. 1553.7 frant, m.s., and ross, j.w., “use of a total ionic strength adjustment buffer for electrode determination of fluoride in water supplies,” anal. chem., vol 40, 1968, p. 1169.3d 1179 99 table 4 determination of precision without distillation usingtable 5 determination of bias without distillation (buffer a)buffersbuffer abuffer bamount added,mg/lamount found,mg/l6 bias6 % biasconcentration,mg/lstsostso0.250.050.0230.0660.022.50.0250.0910.040.035251.210.3560.8960.21825022.23.461.680.800.250.230.0282.52.53+ 0.07+ 1.22524.35 0.65 2.6250246.73.3 1.32table 6 determination of bias without distillation (buffer b)18.2 buffer a for aluminumto approximately 500amount added,mg/lamount found,mg/l6 bias6 % biasml of water, add 84 ml of reagent grade hydrochloric acid(sp gr 1.19), 242 g of tris-(hydroxymethyl)-aminomethane(tham) (also known as 2-amino-2-(hydroxymethyl)-1,3- propanediol), and 230 g of sodium tartrate (na2c4h4o62h 2o). stir to dissolve, and cool to room temperature. transfer the solution to a 1000-ml volumetric flask and dilute to the mark with water.18.3 buffer b for aluminumdissolve 60 g of citric acid monohydrate, 210 g of sodium citrate dihydrate, and 53.5 g of ammonium chloride in 500 ml of water. add 67 ml of ammonium hydroxide (sp gr 0.90). transfer the solution to a1000-ml volumetric flask and dilute to the mark with water.18.4 sodium fluoride solution, standard (1.0 ml = 0.01mg of f)see 11.3.19. calibration19.1 prepare a series of three standards, 0.5, 1.0, and 2.0 mg/l, using the standard fluoride solution (see 18.4). dilute the following volumes to 100 ml:fluoride solution, standard, ml(1.0 ml = 0.01 mg f)concentration, mg f/l5.000.5010.001.0020.002.0019.1.1 for unusual waters containing high concentrations of fluorides, the range of standards may be expanded up to 1000 mg/l, if necessary.19.2 pipet 50 ml of each standard into a 150-ml beaker. using a pipet, add 50 ml of buffer. mix each solution well using a magnetic stirrer.19.3 calibration of ph meterimmerse the ph electrodes in each standard solution, starting with the lowest concentra- tion, and measure the developed potential while mixing. the electrodes must remain in the solution for at least 3 min, or until the reading has stabilized. using semilogarithmic graph paper, plot the concentration of fluoride in milligrams per litre on the logarithmic axis versus the electrode potential devel- oped in the standard on the linear axis, starting with the lowest concentration at the bottom of the scale.19.4 calibration of ise meterfollow the directions of the manufacturer for the operation of the instrument. see 19.1 and19.