BS EN 61619-1997 Insulation liquids - Contamination by polychlorinated biphenyls (PCBs) - Method of determination by capillary column gas chromatography《绝缘液 多氯联苯污染度 毛细管气相色谱测定法》.pdf

1、BRITISH STANDARD BS EN 61619:1997 IEC 1619:1997 Insulating liquids Contamination by polychlorinated biphenyls (PCBs) Method of determination by capillary column gas chromatography The European Standard EN 61619:1997 has the status of a British Standard ICS 29.035.40BSEN61619:1997 This British Standa

2、rd, having been prepared under the directionof the ElectrotechnicalSector Board, was published under the authorityof the Standards Boardand comes intoeffecton 15July 1997 BSI 09-1999 ISBN 0 580 27781 X National foreword This British Standard is the English language version of EN61619:1997. It is ide

3、ntical with IEC1619:1997. The UK participation in its preparation was entrusted to Technical Committee GEL/10, Fluids for electrotechnical applications, which has the responsibilityto: aid enquirers to understand the text; present to the responsible international/European committee any enquiries on

4、the interpretation, or proposals for change, and keep the UKinterests informed; monitor related international and European developments and promulgate them in the UK. A list of organizations represented on this committee can be obtained on request to its secretary. Cross-references Attention is draw

5、n to the fact that Annex ZA lists normative references to international publications with their corresponding European publications. The British Standards which implement these international or European publications may be found in the BSI Standards Catalogue under the section entitled “Internationa

6、l Standards Correspondence Index”, or using the “Find” facility of the BSI Standards Electronic Catalogue. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British St

7、andard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, pages i and ii, theEN title page, pages 2 to 26, an inside back cover and a back cover. This standard has been updated (see copyright date) and may have ha

8、d amendments incorporated. This will be indicated in the amendment table on the inside front cover. Amendments issued since publication Amd. No. Date CommentsBSEN61619:1997 BSI 09-1999 i Contents Page National foreword Inside front cover Foreword 2 Text of EN 61619 3ii blankEUROPEAN STANDARD NORME E

9、UROPENNE EUROPISCHE NORM EN 61619 April 1997 ICS 29.035.40 Descriptors: Electrical insulating materials, liquid electrical insulating materiels, contamination, polychlorinated biphenyls, determination, gas chromatography, capillary columns English version Insulating liquids Contamination by polychlo

10、rinated biphenyls (PCBs) Method of determination by capillary column gas chromatography (IEC 61619:1997) Isolants liquides Contamination par les polychlorobiphnyles (PCB) Mthode dedtermination par chromatographie enphase gazeuse sur colonne capillaire (CEI 61619:1997) Isolierflssigkeiten Verunreinig

11、ung durchpolychlorierte Biphenyle (PCBs) Verfahren zur Bestimmung mittels Kapillar-Gaschromatographie (IEC 61619:1997) This European Standard was approved by CENELEC on 1997-03-11. CENELEC members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving

12、 this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the Central Secretariat or to any CENELEC member. This European Standard exists in three official ver

13、sions (English, French, German). A version in any other language made by translation under the responsibility of a CENELEC member into its own language and notified to the Central Secretariat has the same status as the official versions. CENELEC members are the national electrotechnical committees o

14、f Austria, Belgium, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom. CENELEC European Committee for Electrotechnical Standardization Comit Europen de Normalisation Electrotechnique Europische

15、s Komitee fr Elektrotechnische Normung Central Secretariat: rue de Stassart 35, B-1050 Brussels 1997 CENELEC All rights of exploitation in any form and by any means reserved worldwide for CENELEC members. Ref. No. EN 61619:1997 EEN61619:1997 BSI 09-1999 2 Foreword The text of document 10/379/FDIS, f

16、uture edition1 of IEC61619, prepared by IEC TC10, Fluids for electrotechnical applications, was submitted to the IEC-CENELEC parallel vote and was approved by CENELEC as EN61619 on1997-03-11. The following dates were fixed: Annexes designated “normative” are part of the body of the standard. Annexes

17、 designated “informative” are given for information only. In this standard, Annex A and Annex ZA are normative and Annex B and Annex C are informative. Annex ZA has been added by CENELEC. Endorsement notice The text of the International Standard IEC61619:1997 was approved by CENELEC as a European St

18、andard without any modification. In the official version, for Annex C, Bibliography, the following note has to be added for the standard indicated: Contents Page Foreword 2 1 Scope and object 3 2 Normative reference 3 3 Definitions 3 4 Principle 3 5 Reagents and auxiliary materials 3 6 Apparatus 5 7

19、 Sample 6 8 Chromatograph operating conditions 6 9 Data-processing system 7 10 Checks of instrumental performance 8 11 Procedure 10 12 Test report 14 13 Detection limit 14 14 Precision 14 Annex A (normative) Test mixtures 15 Annex B (informative) General informations 22 Annex C (informative) Bibliog

20、raphy 26 Annex ZA (normative) Normative references to international publications with their corresponding European publications Inside back cover Figure 1 Linearity check 9 Figure A.1 Chromatogram for test mixture 1242/1254/1260 (5.5) 15 Figure B.1 Examples of chromatograms obtained for the three ma

21、in Aroclors 25 Table 1 Typical amounts of the major congeners in Aroclor mixtures 9 Table 2 Reference peaks/congeners 12 Table 3 Congeners for ERRF calibration 13 Table A.1 List of congeners, retention times and relative response factors 17 Table A.2 Elution order of PCB 20 Table B.1 Systematic numb

22、ering of PCB-compounds 22 latest date by which the EN has to be implemented at national level by publication of an identical national standard or by endorsement (dop) 1998-01-01 latest date by which the national standards conflicting with the EN have to be withdrawn (dow) 1998-01-01 IEC 60567 NOTEHa

23、rmonized as EN 60567:1992 (notmodified).EN61619:1997 BSI 09-1999 3 1 Scope and object This International Standard specifies a method for the determination of polychlorinated biphenyl (PCB) concentration in non-halogenated insulating liquids by high-resolution capillary column gas chromatography usin

24、g an electron capture detector (ECD). The method gives the total PCB content and is especially useful when a detailed analysis of PCB congeners is necessary. Other methods, such as IEC60997, may be used when a less detailed analysis is acceptable. The method is applicable to unused, reclaimed (inclu

25、ding dechlorinated and chemically and/or physically treated), or used insulating liquids contaminated by PCBs. 2 Normative reference The following normative document contains provisions which, through reference in this text, constitute provisions of this normative document. At the time of publicatio

26、n, the edition indicated was valid. All normative documents are subject to revision, and parties to agreements based on this International Standard are encouraged to investigate the possibility of applying the most recent editions of the normative document indicated below. Members of IEC and ISO mai

27、ntain registers of current valid International Standards. IEC 60475:1974, Method of sampling liquid dielectrics. 3 Definitions For the purposes of the International Standard, the following definitions apply: 3.1 polychlorinated biphenyl (PCB) a biphenyl substituted by one to ten chlorine atoms NOTEF

28、or legal purposes, congeners with one, two or ten chlorine atoms may be excluded from this definition. 3.2 congener all the chlorine derivatives of biphenyl, irrespective of the number of chlorine atoms, are termed congeners NOTEThere are 209 possible PCB congeners. These are listed inTable B.1. The

29、 congener numbers (IUPAC) 1)are for easy identification; they do not represent the order of chromatographic elution. 4 Principle The PCB congeners are determined by temperature programmed gas chromatography. The chromatograph uses a high-efficiency capillary column to separate the PCBs into single o

30、r small groups of overlapping congeners. The sensitivity of the electron capture detector (ECD) may be reduced by the presence of mineral oil. In this method the sample is diluted100times to reduce this effect to a minimum. A sample preparation (clean-up) procedure is used to remove most of the impu

31、rities likely to interfere with the determination. Reference compounds are included to enable calculation of experimental relative retention times (ERRTs) which are compared to a data file of peak ERRTs to identify individual or groups of unresolved congeners. An internal standard is added for quant

32、ification. Relative response factors (RRF), taken from the data files (9.1), corrected by experimental relative response factors (ERRFs) obtained from reference compounds, are applied to identified peaks to quantify the individual (or groups of) congeners, and the values summed to give total PCB con

33、tent. 5 Reagents and auxiliary materials 5.1 Reagents and standards All reagents and materials, including those for clean-up, shall be free from PCB contamination and compounds responding to the ECD. 1) International Union of Pure and Applied Chemistry.EN61619:1997 4 BSI 09-1999 5.1.1 Solvent Hexane

34、, heptane, cyclohexane or isooctane (2,2,4-trimethylpentane), high purity, free from PCB contamination and low in compounds that respond to the ECD. 5.1.2 Hexachlorobenzene Purity99% at least, used for checking detector sensitivity. 5.1.3 Insulating liquid An insulating liquid, checked to be free fr

35、om PCBs or other interfering substances, of the same type as is present in the sample. 5.1.4 Congener 30 solution (C 30) 10 mg/l in solvent (5.1.1) purchased in solution or prepared from pure material (purity99% at least). 5.1.5 Congener 209 (DCB), decachlorobiphenyl solution 10 mg/l in solvent (5.1

36、.1) purchased in solution or prepared from pure material (purity99% at least). 5.1.6 Calibration solution of selected PCB congeners Certified calibration mixture in solvent (5.1.1) containing at least the following PCB congeners at a concentration of10mg/l each:18,28,31,44,52,101,118,138,149,153,170

37、,180,194 and209 (seeB.3). 5.2 Commercial PCB standards (see B.4) 5.2.1 Solutions of Aroclors 1242, 1254 and 1260 in solvent (5.1.1) Concentration required50mg/l or more, typically1000mg/l. 5.2.2 Solutions of Aroclors 1242, 1254 and 1260 in oil 50 mg/kg solutions of Aroclors 1242,1254 and1260 in unus

38、ed insulating liquid, either purchased as standardized solutions or prepared from pure material. 5.3 Gas chromatography gases 5.3.1 Carrier gas: helium or hydrogen, purity99,99% at least. 5.3.2 Make-up gas: argon/methane,95%/5%. Alternatively,99,99% minimum purity nitrogen can be used. 5.4 Internal

39、standard/reference solutions NOTEStandards should be stored in a cool, dark place. 5.4.1 Internal standard solution 2 (IS 2) 2 mg/l C209 (DCB), 2 mg/l C30. Pipette (5.8.3)5ml of DCB solution (5.1.5) and5ml C30 solution (5.1.4) into a25ml volumetric flask, make up to the mark with solvent (5.1.1). 5.

40、4.2 Internal standard solution 0,5 (IS 0,5) 0,5 mg/l C209 (DCB), 0,5 mg/l C30. Follow 5.4.1 using a100ml volumetric flask. 5.5 Test mixture solution (for system evaluation) Into a 20ml volumetric flask: weigh, to the nearest0,001g,0,50g of 50mg/kg Aroclor 1260, plus0,50g of50mg/kg Aroclor 1254 plus1

41、,00g of 50mg/kg Aroclor 1242 solutions in insulating liquid (5.2.2). Add by pipette1ml of IS2 solution (5.4.1) and make up to volume with solvent. Prior to use this solution shall be treated as per11.1.3. 5.6 Calibration congener mix stock solution Into a20ml volumetric flask: weigh, to the nearest0

42、,001g,2,0g of insulating liquid (5.1.3) and add1ml of the calibration PCB congener mix (5.1.6). Make up to the mark with solvent (5.1.1). 5.7 Congener mix calibration solution (for response factors) Submit5004l of solution (5.6) to the clean-up (11.1.3). The final solution is suitable for the determ

43、ination of relative factors. Prepare a fresh solution monthly.EN61619:1997 BSI 09-1999 5 5.8 Glassware 5.8.1 Volumetric flasks 100, 50, 25, 10 and 5 ml (tolerance better than 0,4 %) 5.8.2 Syringes and pipettes: 500 4l 54l syringe or pipette, 1 4l and 54l gas chromatography precision syringes. 5.8.3

44、Bulb pipettes (volumetric) 1, 2 and 5 ml class A 5.9 Columns and accessories for sample preparation 5.9.1 Commercial or self-packed solid-phase extraction columns: 3 ml silica gel column, adsorbent weight500mg, particle size404m, 3 ml benzenesulphonic acid column, adsorbent weight500mg, particle siz

45、e404m. 5.9.2 Column adapter, for joining two columns 5.9.3 Vacuum manifold column processor optional 6 Apparatus 6.1 Gas chromatograph (GC) A high-resolution gas chromatograph with accurately reproducible oven temperature control, capable, when used with the appropriate column and conditions, of res

46、olving the test mixture (5.5) at least as well as in Figure A.1 (90peaks observed) and of reproducing relative retention times to within 0,0015. The gas lines (carrier gas and make-up gas) shall be fitted with water vapour and oxygen traps. The carrier gas supply system shall be capable of running w

47、ith a50m column at maximum efficiency using He or H 2carrier gas, e.g.adequate column head pressure. The oven temperature programmer shall have a range that can be set to attain the required resolution. 6.1.1 Injector Either an “on-column” injector or a “split/splitless” injector may be used. 6.1.2

48、Columns Either a cross-linked5% phenyl-methyl silicone, stationary phase coated onto fused silica capillary column or a similar chemically bonded phase column. Their dimensions shall be as follows: NOTEFor suitable columns and manufacturers seeB.2. 6.1.3 Detector High-temperature Ni 63 electron capt

49、ure detector (ECD) with adequate sensitivity to give a signal-to-noise ratio greater than20for one picogram of hexachlorobenzene (5.1.2) injected into the column. The detector shall be operated within its linear range. length = 50 m to 60 m; internal diameter = 0,2 mm to 0,35 mm; film thickness = 0,1 4m to 0,25 4m.EN61619:1997 6 BSI 09-1999 6.2 Data-processing system Any data-processing system may be used with suitable software that can be programmed to process the operations shown below. 7 Sample 7.1 Sam