1、BRITISH STANDARD BS EN 13639:2002 Incorporating Corrigendum No.1 Determination of total organic carbon in limestone The European Standard EN 13639:2002 has the status of a British Standard ICS 91.100.10 BS EN 13639:2002 This British Standard, having been prepared under the direction of the Building
2、and Civil Engineering Sector Policy and Strategy Committee, was published under the authority of the Standards Policy and Strategy Committee on 23 July 2002 BSI 17 November 2004 ISBN 0 580 40128 6 National foreword This British Standard is the official English language version of EN 13639:2002, incl
3、uding Corrigendum September 2004. The UK participation in its preparation was entrusted by Technical Committee B/516, Cement and lime, to Subcommittee B/516/12, Sampling and testing, which has the responsibility to: A list of organizations represented on this subcommittee can be obtained on request
4、to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Elect
5、ronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to u
6、nderstand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comp
7、rises a front cover, an inside front cover, the EN title page, pages 2 to 20, an inside back cover and a back cover. The BSI copyright notice displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date Comments 15443 Corrigendum No.1 17 N
8、ovember 2004 Changes to 3.2 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13639 April 2002 ICS 91.100.10 Incorporating corrigendum September 2004 English version Determination of total organic carbon in limestone Dtermination du carbone organique total dans le calcaire Bestimmung des Gesamtge
9、halts an organischem Kohlenstoff in Kalkstein This European Standard was approved by CEN on 23 December 2001. 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 alter
10、ation. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translat
11、ion under the responsibility of a CEN member into its own language and notified to the Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy
12、, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels 2002 CEN All rights of exploitation in any fo
13、rm and by any means reserved worldwide for CEN national Members. Ref. No. EN 13639:2002 EEN 13639:2002 (E) 2 Contents page 1 Scope3 2 Normative references3 3 General requirements for testing.3 4 Reagents.5 5 General apparatus.7 6 Wet oxidation method (reference method) .7 7 Gravimetric furnace oxida
14、tion method (alternative method 1) .9 8 Furnace oxidation infrared detection method (alternative method 2)11 9 Automatic determination methods (alternative methods 3)15 10 Repeatability and reproducibility standard deviation, determination limit .16 11 Test report17 Annex A (informative) Features of
15、 commercial HF combustion/infrared carbon analyzers .18 Annex B (informative) Table B.1 - Assignment of reagents to methods .19 Bibliography 20 EN 13639:2002 (E) 3 Foreword This document EN 13639:2002 has been prepared by Technical Committee CEN/TC 51 “Cement and building limes“, the secretariat of
16、which is held by IBN. 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 October 2002, and conflicting national standards shall be withdrawn at the latest by October 2002. The annexes A and B are inf
17、ormative. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Malta, Netherl
18、ands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom. 1 Scope This European Standard specifies methods for the determination of the total organic carbon content (TOC) in limestone. The standard describes the reference method and alternative methods which can be considered to be
19、equivalent. In the case of a dispute, only the reference method is used. Any other methods may be used provided they are calibrated, either against the reference method or against internationally accepted reference materials, in order to demonstrate their equivalence. 2 Normative references This Err
20、or! Reference source not found. incorporates by dated or undated reference, provisions from other publications. These normative references are cited at the appropriate places in the text and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of
21、these publications apply to this Error! Reference source not found. only when incorporated in it by amendment or revision. For undated references the latest edition of the publication referred to applies (including amendments). ISO 33101, Test sieves Technical requirements and testing - Part 1: Test
22、 sieves of metal wire cloth. ISO 11464, Soil quality Pretreatment of samples for physico-chemical analyses. 3 General requirements for testing 3.1 Number of tests Where the analysis is one of the series subject to statistical control, determination of the total organic carbon content by a single tes
23、t 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). In the case of a dispute, the number of tests for determination of the total organic carb
24、on content shall be two (see also 3.3). EN 13639:2002 (E) 4 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 material tested in
25、 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 material tested i
26、n different laboratories with different operators using different equipment. NOTE Definitions based on ISO 3534-1. The standard deviations of repeatability and reproducibility are expressed in absolute percent. Determination limit- is the content where its relative uncertainty, which is assigned to
27、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. x x Q x x p n t s k x 2 DI f, 0 DI ) ( 1 1 + + = (1) where is the probability level f is the variability (number
28、 of degrees of freedom) Dl Dl x x k = 1is the relative uncertainty n is the number of calibration samples () = = n i i x x x Q 1 2p is the number of analyses of each calibration sample s x0is the standard deviation of the procedure t f,is the quantile of the t-distribution (f = n 2) x i is the analy
29、zed content assigned to a calibration sample x is the arithmetic mean of the contents assigned to all calibration samples x Dlis the determination limit x Dlis half width of the two-side prognosis interval NOTE This determination limit is based on DIN 32645. 3.3 Expression of masses and results Expr
30、ess masses in grams to an accuracy of 0,0005 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, the test shall be repeated. EN 13639:2002 (E) 5 3.4 Bla
31、nk 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 sample preparation Depending on the size of the raw material, a sample of at least 1
32、 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 process shall be modified, if necessary,
33、 to accommodate samples known to contain high contents of volatile organic carbon. 3.6 General test principles In general all procedures consist of the following stages: decarbonation of the original limestone sample; purification of the carrier gas, if it is not of high purified quality; oxidation
34、of the organic carbon matter; purifying of the CO 2produced by oxidation; measurement of the CO 2content. 4 Reagents 4.1 General requirements Use only reagents of analytical quality. References to water mean distilled water, or water of equal purity. Unless otherwise stated percent means percent by
35、mass. The concentrated liquid 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
36、of dilution is always given 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. EN 13639:2002 (E) 6 4.2 Ammonia solution (NH 3 H 2 O) 4.3 Calcium chloride, anhydrous (CaCl 2 ) 4.4 Calibration re
37、agent. Metal, for example iron with known carbon content. 4.5 Carbon dioxide in oxygen, 0,95 vol.-% and 19 vol.-% 4.6 Carrier gases, depending on application: air, oxygen, nitrogen or argon, free of carbon dioxide and hydrocarbons 4.7 Chromic acid. 1)Dissolve 5 g of chromium trioxide (4.8) in 10 ml
38、of water. Add sulfuric acid (4.13) with stirring, until the chromium trioxide, which initially precipitates, is just redissolved. 4.8 Chromium trioxide (CrO 3 )4.9 Concentrated hydrochloric acid (HCI) 4.10 Concentrated hydrogen peroxide (H 2 O 2 ) 4.11 Concentrated nitric acid (HNO 3 ) 4.12 Concentr
39、ated phosphoric acid (H 3 PO 4 ) 4.13 Concentrated sulfuric acid (H 2 SO 4 ) 4.14 Copper (Cu), free of carbon 4.15 Copper 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 (PbCrO 4 ) 4.2
40、0 Magnesium perchlorate (Mg(ClO 4 ) 2 ), anhydrous. Particle size 0,6 mm to 1,2 mm. 4.21 Magnesium sulfate, anhydrous (MgSO 4 ) 4.22 Magnesium turnings according to Grignard (Mg) 4.23 Manganese dioxide (MnO 2 ). Particle size of 0,6 mm to 1,2 mm. 4.24 Oxalic acid dihydrate (C 2 H 2 O 4 2 H 2 O) 1) W
41、arning: 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 working with chromic acids. The use of chromic acid resistant fume cupboards and acid resistant gloves is obligatory. EN 13639:20
42、02 (E) 7 4.25 Oxidation catalyst. Ignited silver permanganate with a composition of approximately AgMnO 4 . 4.26 Oxidizing mixture 1)To 85 ml sulfuric acid (4.13) in a 250 ml beaker add in order 15 ml phosphoric acid (4.12), 20 g phosphorus pentoxide (4.28), 15 g potassium dichromate (4.30), and 1 g
43、 potassium iodate (4.31). Carefully heat the mixture to about 170 C maintaining the temperature for about 5 min and occasionally stirring with a thermometer. Allow the mixture to cool to room temperature and store it in a stoppered bottle. 4.27 Paraffin 4.28 Phosphorus pentoxide (P 2 O 5 ) 4.29 Plat
44、inum (1 %) on alumina pellets (Pt). Particle size 3,2 mm, oxidation catalyst. 4.30 Potassium dichromate (K 2 Cr 2 O 7 ) 4.31 Potassium iodate (KIO 3 ) 4.32 Silver gauze (Ag). Wash commercially available silver gauze with ammonia solution (4.2), nitric acid 1 + 9 (4.17) and hydrogen peroxide (4.10).
45、Rinse the gauze with water between each washing. 4.33 Sodium hydroxide (NaOH) 4.34 Sodium hydroxide (NaOH) on a high surface dark coloured siliceous carrier 4.35 Sodium hydroxide solution. Dissolve 40 g sodium hydroxide (4.33) in water and make up to 1 000 ml. Store in a polyethylene container. 4.36
46、 Sodium iodide (NaI)4.37 Sodium iodide solution. Add 10 ml of hydrochloric acid (4.9) and 150 g of sodium iodide (4.36) into a 1 l volumetric flask and dilute to 1 l with water. 4.38 Zinc wool (Zn) 5 General apparatus 5.1 Balances capable of weighing to an accuracy of 0,0005 g, and of 0,00005 g for
47、alternative method 2, respectively. 5.2 Laboratory ovens capable of maintaining at the following temperatures: (75 5)C; (105 5)C 6 Wet oxidation method (reference method) 6.1 Principle The carbon dioxide in the limestone is driven off by use of phosphoric acid (4.12). The remaining organic carbon is
48、 then oxidized to carbon dioxide with a strong oxidizing reagent mixture (4.26). The liberated carbon dioxide is absorbed on an inorganic carrier impregnated with sodium hydroxide (4.34) in a U-tube. The increase in mass is directly proportional to the organic carbon content in the sample. EN 13639:
49、2002 (E) 8 6.2 Apparatus The apparatus is illustrated in Figure 1. To generate reduced pressure in the apparatus a small vacuum pump or an aspirator is used. The absorption tube (see Figure 1, no. 8) is filled approximately two thirds of its volume with the absorbent for carbon dioxide (4.34) and with magnesium perchlorate (4.20). The absorption tube is then inserted into the apparatus as shown in Figure 1 drawing through it about 4 l of carrier gas (
