1、BRITISH STANDARDBS EN ISO 6143:2006Incorporating amendment no. 1 (renumbers BS ISO 6143:2001 as BS EN ISO 6143:2006)Gas analysis Comparison methods for determining and checking the composition of calibration gas mixturesThe European Standard EN ISO 6143:2006 has the status of a British StandardICS 7
2、1.040.40g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS EN ISO 6143:2006This British Standard, having been prepared under the direction of the Se
3、ctor Committee for Materials and Chemicals, was published under the authority of the Standards Committee and comes into effect on 15 August 2001 BSI 2007ISBN 0 580 38068 8National forewordThis British Standard was published by BSI. It is the UK implementation of EN ISO 6143:2006. It is identical wit
4、h ISO 6143:2001. It supersedes BS 4559-9.1:1988 which is withdrawn.The UK participation in its preparation was entrusted to Technical Committee PTI/15, Natural gas and gas analysis.A list of organizations represented on PTI/15 can be obtained on request to its secretary.This publication does not pur
5、port to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard cannot confer immunity from legal obligations.Amendments issued since publicationAmd. No. Date Comments16904 28 February 2007 Renumbers BS ISO 6143:2001 a
6、s BS EN ISO 6143:2006.EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN ISO 6143August 2006ICS 71.040.40English VersionGas analysis - Comparison methods for determining andchecking the composition of calibration gas mixtures (ISO6143:2001)Analyse des gaz - Mthodes comparatives pour ladtermination et
7、 la vrification de la composition desmlanges de gaz pour talonnage (ISO 6143:2001)Gasanalyse - Vergleichsverfahren zur Bestimmung undberprfung der Zusammensetzung vonKalibriergasgemischen (ISO 6143:2001)This European Standard was approved by CEN on 21 July 2006.CEN members are bound to comply with t
8、he CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the Central Secretariat or
9、 to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the officialversions
10、.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,Slovakia, Slovenia, Spain, Sweden, Swi
11、tzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN
12、 ISO 6143:2006: EForeword The text of ISO 6143:2001 has been prepared by Technical Committee ISO/TC 158 “Analysis of gases” of the International Organization for Standardization (ISO) and has been taken over as EN ISO 6143:2006 by Technical Committee CEN/SS N21 “Gaseous fuels and combustible gas“, t
13、he secretariat of which is held by CMC. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by February 2007, and conflicting national standards shall be withdrawn at the latest by February 2007. Accordi
14、ng to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania
15、, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Endorsement notice The text of ISO 6143:2001 has been approved by CEN as EN ISO 6143:2006 without any modifications. EN ISO 6143:2006Reference numberISO 6143:2001(E
16、)INTERNATIONALSTANDARDISO6143Second edition2001-05-01Gas analysis Comparison methods fordetermining and checking the compositionof calibration gas mixturesAnalyse des gaz Mthodes comparatives pour la dtermination et lavrification de la composition des mlanges de gaz pour talonnageEN ISO 6143:2006ii
17、ISO 1002 All rights rsedevre iiiContents PageForeword.ivIntroduction.v1 Scope 12 Terms and definitions .13 Symbols and abbreviated terms 34 Principle45 General procedure.66 Special procedures147 Test report 14Annex A (normative) Procedures for data evaluation.16Annex B (informative) Examples .23Anne
18、x C (informative) Computer implementation of recommended methods .31Bibliography33EN ISO 6143:2006iv ISO 1002 All rights rsedevreForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISOmember bodies). The work of preparing Internati
19、onal Standards is normally carried out through ISO technicalcommittees. Each member body interested in a subject for which a technical committee has been established hasthe right to be represented on that committee. International organizations, governmental and non-governmental, inliaison with ISO,
20、also take part in the work. ISO collaborates closely with the International ElectrotechnicalCommission (IEC) on all matters of electrotechnical standardization.International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 3.Draft International Standards adopt
21、ed by the technical committees are circulated to the member bodies for voting.Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote.Attention is drawn to the possibility that some of the elements of this International Standard may be the subj
22、ect ofpatent rights. ISO shall not be held responsible for identifying any or all such patent rights.International Standard ISO 6143 was prepared by Technical Committee ISO/TC 158, Analysis of gases,tocanceland replace the first edition (ISO 6143:1981), of which the methods for the design and evalua
23、tion of calibrations ofanalytical systems have been updated and a method for estimating the uncertainty of the composition of calibrationgas mixtures has been added. It also cancels and replaces ISO 6711:1981, of which entirely new methods forchecking the composition of calibration gases have been s
24、pecified, thus replacing the method which is no longer inuse.Annex A forms a normative part of ISO 6143. Annexes B and C are for information only.EN ISO 6143:2006 ISO 1002 All rights rsedevre vIntroductionIn gas analysis, calibration of analytical systems, as specified in the first edition of ISO 61
25、43, has largely beenconfined to the determination of a straight line through the origin, or of a straight-line segment, using only theminimum number of calibration standards (one for a straight line through the origin, two for a line segment). Theapproach adopted in the revision, relating to calibra
26、tion as well as to uncertainty evaluation, goes far beyond thissimple scheme byGbe including non-linear response curves and/or functions,Gbe replacing interpolation by regression,Gbe taking into account the uncertainty on the calibration standards,Gbe including validation of calculated response curv
27、es and/or functions,Gbe calculating uncertainties by uncertainty propagation.As a consequence of adopting non-linear response models, advanced regression techniques (errors in bothvariables) and uncertainty propagation, the main calculation procedures can only be performed on a computer,using a spec
28、ific program. Such a program is available (see annex C). As an alternative, sufficient information isgiven in the document to enable the user to develop a program on his own.EN ISO 6143:2006blank ISO 1002 All rights rsedevre 1Gas analysis Comparison methods for determining andchecking the compositio
29、n of calibration gas mixtures1 ScopeThis International Standard provides methods forGbe determining the composition of a calibration gas mixture by comparison with appropriate reference gasmixtures,Gbe calculating the uncertainty of the composition of a calibration gas mixture in relation to the kno
30、wn uncertainty ofthe composition of the reference gas mixtures with which it was compared,Gbe checking the composition attributed to a calibration gas mixture by comparison with appropriate reference gasmixtures,Gbe comparing the composition of several calibration gas mixtures, e.g. for the purpose
31、of comparing differentmethods of gas mixture preparation, or for testing consistency among gas mixtures of closely relatedcomposition.NOTE In principle, the method described in this document is also applicable to the analysis of (largely) unknown samplesinstead of prospective calibration gas mixture
32、s (i.e. gas mixtures which are intended for use as calibration gas mixtures). Suchapplications, however, require appropriate care and consideration of additional uncertainty components, for example concerningthe effect of matrix differences between the reference gases used for calibration and the an
33、alysed sample.2 Terms and definitionsFor the purposes of this International Standard, the following terms and definitions apply.2.1compositioncharacteristic of a gas mixture given by the kind and content of each specified mixture component (analyte) and thecomposition of the complementary gas (matri
34、x)NOTE In this International Standard, the analyte content is specified as a mole fraction, exclusively. Mole fractions havethe advantage of being perfectly independent of the pressure and the temperature of the gas mixture. Therefore their use isrecommended. However, for specific measuring systems,
35、 other composition measures (e.g. mass concentrations) may be moreappropriate. Their use then requires due care concerning the dependence on pressure and temperature.2.2comparison methodmethod for determining the content of a specified gas mixture component (analyte) by measuring an instrumentalresp
36、onseNOTE Comparison of measuring systems requires calibration, in which the relationship between response and analytecontent is established. This is achieved by measuring the response to known values of analyte content provided by referencegas mixtures.EN ISO 6143:20062 ISO 1002 All rights rsedevre2
37、.3calibrationset of operations that establish, under specified conditions, the relationship between values of quantities indicatedby a measuring instrument or measuring system, or values represented by a material measure or referencematerial, and the corresponding values realized by standardsVIM2.4r
38、esponse functionfunctional relationship between instrumental response and analyte contentNOTE 1 The response function can be expressed in two different ways as a calibration function or an analysis function,depending on the choice of the dependent and the independent variable.NOTE 2 The response fun
39、ction is conceptual and cannot be determined exactly. It is determined approximately throughcalibration.2.4.1calibration functioninstrumental response expressed as a function of analyte content2.4.2analysis functionanalyte content expressed as a function of instrumental response2.5uncertainty of mea
40、surementparameter, associated with the result of a measurement, that characterizes the dispersion of the values that canreasonably be attributed to the measurandGUMNOTE In keeping with the GUM, in this International Standard the uncertainty of the composition of a gas mixture isexpressed as a standa
41、rd uncertainty, i.e. as a single standard deviation.2.6traceabilityproperty of the result of a measurement or the value attributed to a standard whereby it can be related to statedreferences, usually national or international standards, through an unbroken chain of comparisons all having stateduncer
42、taintiesVIM2.7measurement standardmaterial measure, measuring instrument, reference material, or measuring system, intended to define, realize,conserve, or reproduce a unit or one or more values of a quantity to serve as a referenceVIM2.8reference standardstandard, generally having the highest metro
43、logical quality available at a given location or in a given organization,from which measurements made there are derivedVIMEN ISO 6143:2006 ISO 1002 All rights rsedevre 32.9working standardstandard that is used routinely to calibrate or check material measures, measuring instruments or referencemater
44、ialsVIMNOTE A working standard is usually calibrated against a reference standard.2.10reference materialmaterial or substance one or more of whose property values are sufficiently homogeneous and well established tobe used for the calibration of an apparatus, the assessment of a measuring method, or
45、 for assigning values tomaterialsISO Guide 302.11calibration gas mixturegas mixture whose composition is sufficiently well established and stable to be used as a working standard ofcomposition2.12reference gas mixturegas mixture whose composition is sufficiently well established and stable to be use
46、d as a reference standard ofcomposition3 Symbols and abbreviated termsajparameters of the calibration function F ( j = 0, 1, ., N)bjparameters of the analysis function G ( j = 0, 1, ., N)D sensitivity matrixF calibration function, y=F(x), for the specified analyteG analysis function, x=G(y), for the
47、 specified analytek coverage factorL limit of detectionMcal(sample of) calibration gas mixtureMref(sample of) reference gas mixtureQ transform matrixS sum of weighted squared deviationsSresresidual sum of weighted squared deviationst Students t-factorU(q) expanded uncertainty of an estimated quantit
48、y q, U(q) =ku(q)EN ISO 6143:20064 ISO 1002 All rights rsedevreu(q) uncertainty of an estimated quantity q, expressed as a standard deviation (standard uncertainty)u(p,q) covariance of two estimated quantities p and qu2(q) variance of an estimated quantity qV variance/covariance matrixW half-width of
49、 a confidence rangex mole fraction of the specified analyte(xi, yi) calibration points (i = 1, 2, ., n)G28 G29 , iixy adjusted calibration points (i = 1, 2, ., n)y instrumental response of the specified analyteZ normal distribution percentage pointG64 relative analytical accuracyG67 dilution factorG47 measure of goodness-of-fit4PrincipleThe composition of a gas mixture is determined by separate determination of the mole fraction of every specifiedanalyte. Therefore the procedure for determining the mole fraction of only on
