1、Determination of total organic carbon in limestoneBS EN 13639:2017BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06EUROPEANSTANDARDNORME EUROPENNE EUROPISCHE NORMEN 13639 September 2017ICS 91.100.10 Supersedes EN 13639:2002EnglishVersionDetermination of total organic
2、carbon in limestoneDetermination du carbone organique total dans le calcaireBestimmung des Gesamtgehalts an organischem Kohlenstoff in KalksteinThis European Standard was approved by CEN on 26 June 2017.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the con
3、ditions for giving thisEuropean Standard the status of a national standard without any alteration.Up-to-date lists and bibliographical referencesconcerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists
4、in three official versions (English, French, German). A version in any other language made bytranslation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC ManagementCentre has the same status as the officialversions.CEN members are the nationalstandards b
5、odies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, S
6、lovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGCEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reservedw
7、orldwide for CENnational Members.Ref. No. EN 13639:2017 ENational forewordThis British Standard is the UK implementation of EN 13639:2017. It supersedes BS EN 13639:2002, which is withdrawn.The UK participation in its preparation was entrusted to Technical Committee B/516/12, Sampling and testing.A
8、list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2017 Published by BSI Standard
9、s Limited 2017ISBN 978 0 580 87896 1ICS 91.100.10Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 October 2017.Amendments/corrigenda issued since publicationDa
10、te Text affectedBRITISH STANDARDBS EN 13639:2017EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13639 September 2017 ICS 91.100.10 Supersedes EN 13639:2002English Version Determination of total organic carbon in limestone Determination du carbone organique total dans le calcaire Bestimmung des
11、Gesamtgehalts an organischem Kohlenstoff in Kalkstein This European Standard was approved by CEN on 26 June 2017. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any a
12、lteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language
13、made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Es
14、tonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTE
15、E FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13639:2017 EBS EN 13639:2017E
16、N 13639:2017 (E) 2 Contents Page European foreword . 4 1 Scope 5 2 Normative references 5 3 General requirements for testing 5 3.1 Number of tests 5 3.2 General statistical terms 5 3.3 Expression of masses and results 6 3.4 Blank determinations 6 3.5 Sampling and sampling preparation 6 3.6 General t
17、est principles 6 4 Reagents . 7 5 General apparatus 9 5.1 Balances 9 5.2 Laboratory ovens 9 5.3 Crucibles 10 6 Gravimetric method with wet oxidation (reference method) . 10 6.1 Principle 10 6.2 Apparatus 10 6.3 Procedure 11 6.4 Calculation 12 7 Gravimetric method with furnace oxidation (alternative
18、method No. 1) . 12 7.1 Principle 12 7.2 Apparatus 12 7.3 Procedure 14 7.4 Calculation 14 8 Infrared detection method with furnace oxidation (low temperature) (alternative method No. 2) 15 8.1 Principle 15 8.2 Apparatus 15 8.3 Procedure 17 8.4 Calculation 18 9 Infrared detection or conductivity metho
19、ds with furnace oxidation (high temperature): procedure A (alternative method No. 3) 19 9.1 Principle 19 9.2 Apparatus 19 9.3 Procedure 20 10 Infrared detection or conductivity methods with furnace oxidation (high temperature): procedure B (alternative method No. 4) 21 10.1 Principle 21 10.2 Apparat
20、us 21 10.3 Procedure 21 BS EN 13639:2017EN 13639:2017 (E) 3 11 Repeatability and reproducibility standard deviation, determination limit . 22 12 Test report 22 Annex A (informative) Features of commercial HF (High Frequency) combustion/infrared carbon analyzers . 23 A.1 Combustion . 23 A.2 Infrared
21、gas analyser 24 Annex B (informative) Assignment of reagents to methods 25 Bibliography . 27 BS EN 13639:2017EN 13639:2017 (E) 4 European foreword This document (EN 13639:2017) has been prepared by Technical Committee CEN/TC 51 “Cement and building limes”, the secretariat of which is held by NBN. Th
22、is 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 March 2018, and conflicting national standards shall be withdrawn at the latest by March 2018. Attention is drawn to the possibility that some of the
23、elements of this document may be the subject of patent rights. CEN shall not be held responsible for identifying any or all such patent rights. This document supersedes EN 13639:2002. In comparison to EN 13639:2002, the following change has been made: In Clause 10 a new alternative method, Alternati
24、ve method No. 4, developed in Sweden, has been included. According to the CEN-CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Fi
25、nland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 13639:2017EN 136
26、39:2017 (E) 5 1 Scope This European Standard specifies methods for the determination of the total organic carbon content (TOC) in limestone. NOTE This method covers the determination of TOC in 1 %. The standard describes the reference method and alternative methods that can be considered to be equiv
27、alent. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including an
28、y amendments) applies. ISO 3310-1, Test sieves Technical requirements and testing Part 1: Test sieves of metal wire cloth ISO 11464, Soil quality Pretreatment of samples for physico-chemical analysis 3 General requirements for testing 3.1 Number of tests Where the analysis is one of the series subje
29、ct to statistical control, determination of the total organic carbon content by a single test shall be the minimum required. Where the analysis is not part of a series subject to statistical control, the number of tests for determination of the total organic carbon content shall be two (see also 3.3
30、). In case of dispute, only the reference method is used. In case of dispute, the number of tests for determination of the total organic carbon content shall be two (see also 3.3). Any other method may be used provided it is calibrated, either against the reference method or against internationally
31、accepted reference materials, in order to demonstrate its equivalence. 3.2 General statistical terms Repeatability standard deviation - the standard deviation of test results obtained under repeatability conditions where independent test results are obtained with the same method on identical materia
32、l tested in the same laboratory by the same operator using the same equipment within short intervals of time. Reproducibility standard deviation - the standard deviation of test results obtained under reproducibility conditions where test results are obtained with the same method on identical materi
33、al tested in different laboratories with different operators using different equipment. NOTE Definitions are based on ISO 3534-1 1. The standard deviations of repeatability and reproducibility are expressed in absolute percent. Determination limit (Formula (1) - is the content where its relative unc
34、ertainty, which is assigned to a fixed probability level, and defined as the quotient of the half of a two-side prognosis interval and the content to be assigned to the determination limit, is equal to a pre-set value. BS EN 13639:2017EN 13639:2017 (E) 6 2.()11DlDl xD fxxxx ks tnp Q= + (1) where: is
35、 the probability level f is the variability (number of degrees of freedom) DlDlxxk=1is the relative uncertainty =niix xxQ12)( is the number of calibration samples n number of test results p is the number of analyses of each calibration sample sxD is the standard deviation of the procedure tf is the
36、quantile of the t-distribution (f = n 2) xiis the analysed content assigned to a calibration sample x is the arithmetic mean of the contents assigned to all calibration samples xDlis the determination limit xDl is half width of the two-side prognosis interval NOTE This determination limit is based o
37、n DIN 32645 2. 3.3 Expression of masses and results Express masses in grams to an accuracy of 0,000 5 g. Express the results as a percentage to at least two decimal places, if the difference between the individual test results exceeds two times the repeatability standard deviation given in Clause 10
38、, the test shall be repeated. 3.4 Blank determinations Carry out a blank determination without a sample following the same procedure and using the same amounts of reagents. Correct the results obtained for the analytical determination. 3.5 Sampling and sampling preparation Depending on the size of t
39、he raw material, a sample of at least 1 kg up to 10 kg shall be taken by the procedure described in ISO 11464, dried, crushed, reduced and ground to form a representative laboratory sample for analysis. The laboratory sample shall pass a sieve of 90 m mesh size conforming to ISO 3310-1. The drying p
40、rocess shall be modified, if necessary, to accommodate samples known to contain high contents of volatile organic carbon. 3.6 General test principles In general, all the methods consist of the following procedures: a) decarbonation of the original limestone sample; b) purification of the carrier gas
41、, if it is not of high purified quality; BS EN 13639:2017EN 13639:2017 (E) 7 c) oxidation of the organic carbon matter; d) purifying of the CO2produced by oxidation; e) measurement of the CO2content. 4 Reagents 4.1 General requirements Application of this standard involves the use of hazardous subst
42、ances. There are national and European regulations and provisions on requirements for occupational health and safety. Use only reagents of analytical quality. References to water mean distilled water, or water of equal purity. Unless otherwise stated percent means percent by mass. The concentrated l
43、iquid reagents used in this standard have the following densities () in grams per cubic centimetre at 20 C: ammonia solution 0,88 to 0,91 hydrochloric acid 1,18 to 1,19 hydrogen peroxide 1,11 nitric acid 1,40 to 1,42 phosphoric acid 1,71 to 1,75 sulfuric acid 1,84 The degree of dilution is always gi
44、ven as a volumetric sum, for example: dilute hydrochloric acid 1 + 2 means that 1 volume of concentrated hydrochloric acid is to be mixed with 2 volumes of water. 4.2 Ammonia solution (NH3 H2O) 4.3 Calcium chloride, anhydrous (CaCI2) 4.4 Calibration reagent, metal For example iron with known carbon
45、content. 4.5 Carbon dioxide in oxygen Concentrations, 0,95 vol.% and 19 vol.% 4.6 Carrier gases Air, oxygen, nitrogen or argon, free of carbon dioxide and hydrocarbons, depending on application. 4.7 Chromic acid Dissolve 5 g of chromium trioxide (4.8) in 10 ml of water. Add sulfuric acid (4.13) with
46、 stirring, until the chromium trioxide, which initially precipitates, is just re-dissolved. BS EN 13639:2017EN 13639:2017 (E) 8 WARNING Chromic acid and its mixtures with sulfuric acid, may cause cancer. Also the vapour phase is dangerous. It is therefore necessary to take special precautions when w
47、orking with chromic acids. 4.8 Chromium trioxide (CrO3) 4.9 Concentrated hydrochloric acid (HCI) 4.10 Concentrated hydrogen peroxide (H2O2) 4.11 Concentrated nitric acid (HNO3) 4.12 Concentrated phosphoric acid (H3PO4) 4.13 Concentrated sulfuric acid (H2SO4) 4.14 Copper (Cu), free of carbon 4.15 Cop
48、per oxide (CuO) Particle size of 0,6 mm to 1,2 mm 4.16 Dilute hydrochloric acid 1 + 5 4.17 Dilute nitric acid 1 + 9 4.18 Iron (Fe), free of carbon 4.19 Lead chromate (PbCrO4) 14.20 Magnesium perchlorate (Mg(CIO4)2), anhydrous Particle size 0,6 mm to 1,2 mm. 4.21 Magnesium sulfate, anhydrous (MgSO4)
49、4.22 Magnesium turnings according to Grignard (Mg) 4.23 Manganese dioxide (MnO2) Particle size of 0,6 mm to 1,2 mm. 4.24 Oxalic acid dihydrate (C2H2O4 2H2O) 4.25 Oxidation catalyst Ignited silver permanganate with a composition of approximately (AgMnO4). 1Where substances are listed in REACH Regulation Annex XIV List of substances subject to authorisation, Article 56(3) of REACH provides a generic exemption from authorisation for listed substances for use in scientific research and development. Scientific research and development includes us
