1、Designation: D3609 00 (Reapproved 2014)Standard Practice forCalibration Techniques Using Permeation Tubes1This standard is issued under the fixed designation D3609; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last r
2、evision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This practice describes a means for using permeationtubes for dynamically calibrating instruments, analyzers, andanalytical
3、procedures used in measuring concentrations ofgases or vapors in atmospheres (1, 2).21.2 Typical materials that may be sealed in permeation tubesinclude: sulfur dioxide, nitrogen dioxide, hydrogen sulfide,chlorine, ammonia, propane, and butane (1).1.3 The values stated in SI units are to be regarded
4、 asstandard.1.4 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 determine the applica-bility of regulatory limitations prior to use.2.
5、Referenced Documents2.1 ASTM Standards:3D1356 Terminology Relating to Sampling and Analysis ofAtmospheresD3195 Practice for Rotameter Calibration3. Terminology3.1 DefinitionsRefer to Terminology D1356.4. Summary of Practice4.1 A liquefiable gas, when enclosed in an inert plastic tube,escapes by perm
6、eating the tubing wall at a constant,reproducible, temperature-dependent rate.4.2 Permeation tubes are calibrated gravimetrically, with theweight loss of the tube equated to the weight of the escapingmaterial.4.3 Permeation tubes are held at constant temperature in acarrier-gas stream of dry air or
7、nitrogen to produce a gasconcentration dependent on the permeation rate and the flow ofthe carrier gas.5. Significance and Use5.1 Most analytical methods used in air pollutant measure-ments are comparative in nature and require calibration orstandardization, or both, often with known blends of the g
8、as ofinterest. Since many of the important air pollutants are reactiveand unstable, it is difficult to store them as standard mixtures ofknown concentration for extended calibration purposes. Analternative is to prepare dynamically standard blends as re-quired. This procedure is simplified if a cons
9、tant source of thegas of interest can be provided. Permeation tubes provide thisconstant source, if properly calibrated and if maintained atconstant temperature. Permeation tubes have been specified asreference calibration sources, for certain analytical procedures,by the Environmental Protection Ag
10、ency (3).6. Interferences and Precautions6.1 Permeation tubes are essentially devices to provide aconstant rate of emission of a specific gaseous substance overperiod of time. They consist of a two-phase (gas-liquid) systemto maintain a constant vapor pressure (at constant temperature)which is the d
11、riving force for emission of the gas through asemipermeable membrane (tube walls). They can be expectedto maintain a constant emission rate that is temperaturedependent as long as a significant amount of liquid is presentin the device. The liquid shall be pure, else its composition maychange during
12、the life time of the tube, due to differentialevaporation, with consequent vapor pressure changes. Caremust also be exercised that the diffusion membrane (tubewalls) is not damaged or altered during use. The contents ofpermeation tubes are under relatively high pressure.Accordingly, there is the pos
13、sibility of violent rupture of tubewalls under high temperature exposure. Permeation rates havetemperature coefficients up to 10 % per degree Celsius. Whentemperature coefficients are large, above 3 % per degreeCelsius, stringent temperature control is required. Furthermorepermeation tubes exhibit t
14、emperature hysteresis so that theymust be temperature equilibrated from 2 to 24 h before use,depending upon the temperature differential between storageand use (4). It is important that permeation tubes are filled with1This practice is under the jurisdiction of ASTM Committee D22 on Air Qualityand i
15、s the direct responsibility of Subcommittee D22.01 on Quality Control.Current edition approved Sept. 1, 2014. Published September 2014. Originallyapproved in 1977. Last previous edition approved in 2010 as D3609 00 (2010).DOI: 10.1520/D3609-00R14.2The boldface numbers in parentheses refer to a list
16、of references at the end ofthis standard.3For 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.Copyright ASTM Inter
17、national, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1anhydrous constituents of high purity. They shall be handledwith care to minimize contact with moisture, oil, and foreignsubstances.6.2 Sulfur dioxide (SO2) permeation tubes are relativelyinsensitive to int
18、erferences.6.3 Nitrogen dioxide (NO2) permeation tubes are sensitiveto moisture, hence they should be stored in dry atmospheresand used with relatively dry carrier gases (10 % relativehumidity). Permeation of moisture into the contents of a tubemay damage the walls and also cause progressive decreas
19、es inthe permeation rate. Moisture incorporated in the contentsduring manufacture can cause the same effect (4).6.4 Hydrogen sulfide (H2S) permeation tubes may turnwhite during use in the presence of oxygen because of inversepermeation and formation of collodial sulfur. This phenom-enon may affect t
20、he permeation rate, if severe, hence is areason for recalibration. However, in an inert gas stream, thetubes are relatively stable.6.5 Materials of construction shall be compatible with thecontents of the tube. For instance, some fluorocarbons maycause FEP tubes to swell and possibly to rupture.7. A
21、pparatus7.1 Permeation Tube sized in accordance with and cali-brated to concentrations needed or expected for the analysismethod. The user should check calibration as described inSection 9.1.7.2 Flow and Temperature Control SystemPrepare orpurchase a system that will dry the carrier gas, and control
22、 andmeasure its flow as it passes over the permeation tube that isbeing held at constant temperature. If lower concentrations aredesired, a second gas supply (diluent gas) with its control andmeasurement devices may be needed to mix with the gas fromthe permeation tube chamber. Equipment of this kin
23、d isavailable commercially. A typical system contains a thermo-electrically temperature-controlled permeation tube chamberwith temperature control within 60.1C over the range from15 to 35C. Such equipment is well suited to field usage.7.3 A typical system for laboratory use that can be as-sembled fr
24、om readily available parts is shown schematically inFig. 1. The parts required are described in the followingsubsections.7.3.1 FlowmetersSeveral, sufficient to cover the rangefrom 0 to 15 L/min, calibrated by Practice D3195.7.3.2 Copper TubingApproximately 1 m long 3 ft by6.25 mm 0.25 in. in outside
25、 diameter for use as a heatexchanger in the water bath.7.3.3 Ball Joints (Ungreased) and Tubing, for the necessaryconnections. Butt seals may also be used made with inertmaterials such as polyethylene.7.3.4 Mixing Bulb, to ensure adequate mixing of the perme-ated gas and the diluent gas stream. A Kj
26、eldahl trap isrecommended.7.3.5 Long Condenser, with large bore in which a thermom-eter and a permeation tube can be inserted.7.3.6 Temperature Controlled Water BathAbout 8-L 2-gal capacity, capable of 60.1C or better water temperaturecontrol, with a variable temperature control range from about15 t
27、o 35C, preferably equipped with a positive displacementtype recirculating pump with at least 1-L/min liquid flow rateto supply water to the condenser.NOTE 1This system has the advantage of smaller uncertainty of the temperature of the permeation tube.FIG. 1 Optional System for Laboratory Use of a Pe
28、rmeation TubeD3609 00 (2014)27.3.7 Thermometer, ASTM No. 91C or equivalent, cali-brated to 60.1C.7.3.8 Mercury Barometer.7.4 An alternate system is shown in Fig. 2. It has theadvantage of lower uncertainty of the temperature of thepermeation tube. The required parts are described in the figure.8. Re
29、agents and Materials8.1 Carrier Gas or Diluent Gas for Flow Over PermeationTubeCylinder of dry nitrogen or pure, dry air, or purifiedroom air (charcoal and drying agentinert air mover).8.1.1 Drier, indicating type and should be discarded whencolor changes.8.2 Diluent Gas for Blending with Carrier St
30、ream Down-stream from Permeation Tube, free from impurities that wouldconsume test substances.9. Calibration of Permeation Tubes9.1 Permeation tubes may be calibrated gravimetrically bymeasurement of the weight loss occurring during storage at aconstant temperature (4, 5). A slow stream of dry air o
31、rnitrogen shall flow over the tube during the calibration period.A specially constructed constant temperature chamber may beused or, if more convenient, the weight loss occurring duringuse of the tube in the actual flow system (7.2 and 7.3) can bemeasured. In the latter case, place the tube in its c
32、hamber(condenser) and run the system as described in Section 10.Remove the tube at 24-h intervals and weigh on a semimicroanalytical balance. Handle the tube with gloves or forceps tominimize pickup of moisture or grease. Remove the tube foronly the minimum time required for the weighing.Furthermore
33、, it is advisable to conduct the weighings when therelative humidity does not exceed 50 %. Record the weighingsto the nearest 0.01 mg. Because NO2permeation tubes maypick up moisture on exposure to air, they may need to beweighed on a rigid time schedule to reproduce any masschanges as a result of t
34、his cause (5). Repeat the weighingoperation at scheduled intervals and plot the gross weightagainst elapsed time in minutes. The slope expressed asmicrograms per minute represents the output of the tube. Thetotal time usually needed to calibrate at a given temperatureshould not be less than five day
35、s. Alternatively, linear regres-sion analysis may be used to determine the permeation rate.Record measurements of permeation rates at several tempera-tures and plot the results on semilog paper to obtain the outputat any temperature within the calibration range.As a precautionagainst defective seals
36、, check the first calibration after approxi-mately two weeks; it should be within 2 % of the initial value.If 2 % cannot be achieved, reject the tube.NOTE 1While permeation tube life may be extended by refrigeratedstorage, it is suggested to store tubes at operating (or room) temperatureto avoid exc
37、essive preconditioning time.9.2 The frequency of recalibration will depend upon type ofpermeation tube, the quality of its construction and the careexercised in its use.9.2.1 Experience at the National Institute of Standards andTechnology, with standard reference material permeation tubeshas indicat
38、ed the following:9.2.1.1 SO2Permeation TubesCalibration is valid for oneyear or until 90 % of the liquid has permeated, whichevercomes first;9.2.1.2 NO2Permeation TubeCalibration is valid for sixmonths or until 90 % of the originally contained liquid haspermeated, whichever comes first.9.2.2 There h
39、as been insufficient experience in the use ofother kinds of permeation tubes as calibration standards topermit general statements. For such tubes, it is recommendedNOTE 1This system is constructed from readily available laboratory equipment.NOTE 2WarningIf the room temperature is significantly diffe
40、rent from that of the water bath, a small difference in temperature between the bathand the condensor containing the permeation tube can exist. In this event, the temperature indicated by the thermometer in the condensor should be usedas that of the permeation tube, rather than that of the water bat
41、h.FIG. 2 Typical System for Laboratory UseD3609 00 (2014)3that they be recalibrated immediately before use and at periodicintervals during use to establish any trends that may occur.10. Procedure10.1 Set up the flow system as described in Section 7 andequilibrate at constant temperature.10.2 The con
42、centration produced will depend upon the flowrate of the gas and the permeation rate. The latter depends inturn on the temperature of the permeation tube. Establish gasflow rates to produce concentrations desired, as calculated bythe expression shown in 11.1. F1is conveniently maintained at0.05 to 0
43、.1 L/min. F2may be any convenient value typicallyfrom 0.2 to 15 L/min.10.3 For commercially available equipment, follow themanufacturers instructions, which must be consistent with andmeet all the requirements of 10.1 and 10.2.10.4 Use output of the flow system to calibrate instruments,analyzers, or
44、 methods in the conventional manner.11. Calculation11.1 Primary Calculations:11.1.1 Determine the concentration of the gas mixture inparts per million by volume as follows:Cppmv!5 R/MW! 3 MV/F! (1)where:Cppm(v)= concentration in ppm by volume at 25C and 101.3kPa,R = permeation rate (gravimetric) g/m
45、in, correspond-ing to temperature of permeation tube,MV = molar volume (24.47 L at 25C and 101.3 kPa),F = F1+ F2= total flow rate of gas, L/min,F1= flow rate of carrier gas passing over permeationtube, L/min,F2= flow rate of diluent gas, L/min, andMW = molecular weight of the permeand.NOTE 2All calc
46、ulations made at operating temperatures and pres-sures.11.1.2 Concentrations may be reported in terms of mass andvolume, Cm, expressed in g/m3as follows:Cm5 Cppmv!3MW 3 1000/24.47! (2)3P/101.3! 3 298.15/t1273.15!#where:P = atmospheric pressure, kPa (mm Hg) andt = ambient temperature, C.11.2 Secondar
47、y Calculations:11.2.1 For convenience, standard conditions are establishedat 101.3 kPa (760 mm Hg) and 25C. This conforms with mostof the ASTM methods for atmospheric sampling and analysisthat involve volumetric corrections. Correction of all volumesto these conditions is done as follows:Vs5 V 3 P/1
48、01.3! 3 298.15/t1273.15!# (3)where:Vs= gas volume, L at STP,V = measured volume in, L,P = barometric pressure, kPa (mm Hg), andt = measured temperature, C.NOTE 3If pressure measured is in mm Hg, the equation is the sameexcept 101.3 is replaced by 760 and the value for P in mm Hg is inserted.11.2.2 D
49、ilution air flows may be corrected to standardconditions as follows:Fs5 F 3 P/101.3! 3 298.15/t1273.15!# (4)where:Fs= flow rate at standard conditions, L/min,F = measured rate of gas flow over the permeation tube,L/min,t = measured temperature, C, andP = barometric pressure, kPa (mm Hg).12. Precision and Bias12.1 The sources of error in the use of permeation devicesfor calibration purposes are evident from an inspection of therelationships given in Section 10.12.1.1 An uncertainty of 1 % in F will produce a corre-sponding uncertain
