SIST EN 13639:2017

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Bestimmung des Gesamtgehalts an organishchem Kohlenstoff in KalksteinDetermination du carbone organique total dans le calcaireDetermination of total organic carbon in limestone91.100.10Cement. Mavec. Apno. MaltaCement. Gypsum. Lime. MortarICS:Ta slovenski standard je istoveten z:EN 13639:2017SIST EN 13639:2017en01-december-2017SIST EN 13639:2017SLOVENSKI
STANDARDSIST EN 13639:2004/AC:2004SIST EN 13639:20041DGRPHãþD

EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 13639
September
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{ sä s r rä s r Supersedes EN
s u x u {ã t r r tEnglish Version
Determination of total organic carbon in limestone Determination du carbone organique total dans le calcaire
Bestimmung des Gesamtgehalts an organischem Kohlenstoff in Kalkstein This European Standard was approved by CEN on
t x June
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egulations which stipulate the conditions for giving this European Standard the status of a national standard without any alterationä Upætoædate lists and bibliographical references concerning such national standards may be obtained on application to the CENæCENELEC Management Centre or to any CEN memberä
translation under the responsibility of a CEN member into its own language and notified to the CENæCENELEC Management Centre has the same status as the official versionsä
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t r s y CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Membersä Refä Noä EN
s u x u {ã t r s y ESIST EN 13639:2017

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 test 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 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 methods 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 Apparatus . 21 10.3 Procedure. 21 SIST EN 13639:2017

Features of commercial HF (High Frequency) combustion/infrared carbon analyzers . 23 A.1 Combustion . 23 A.2 Infrared gas analyser . 24 Annex B (informative)
Assignment of reagents to methods . 25 Bibliography . 27
is the probability level f is the variability (number of degrees of freedom) DlDlxxk∆=1 is the relative uncertainty ∑=−=niixxxQ12)( 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 t is the quantile of the t-distribution (f = n
xi is the analysed content assigned to a calibration sample x is the arithmetic mean of the contents assigned to all calibration samples xDl is the determination limit
¿xDl is half width of the two-side prognosis interval
NOTE This determination limit is based on 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, 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 the 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 µm mesh size conforming to ISO 3310-1. The drying process 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, if it is not of high purified quality; SIST EN 13639:2017

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 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. 4.2 Ammonia solution (NH3 × H2O) 4.3 Calcium chloride, anhydrous (CaCI2) 4.4 Calibration reagent, metal For example iron with known carbon 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 stirring, until the chromium trioxide, which initially precipitates, is just re-dissolved. SIST EN 13639:2017

1 Where 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 use of listed substances as reagents for analysis and quality control purposes as long as use is carried out under controlled conditions and the amount does not exceed one tonne per year, per legal entity.
See FAQ [585] on ECHA's website. SIST EN 13639:2017

Key 1 drying tower for carrier gas containing a carbon dioxide absorbent (4.34) 2 safety trap 3 inlet tube for the oxidising mixture (4.26) with glass rod stopper 4 150 ml round bottom distillation flask 5 100 ml sharp bottomed flask with 50 ml chromic acid (4.7) 6 absorption tube filled (in order upwards) with zinc wool (4.38), lead chromate (4.19) and silver gauze (4.32). The materials are fixed in place with cotton wool plugs 7 absorption tube filled with magnesium perchlorate (4.20), fixed in place with cotton wool 8 absorption tube with a total volume of approximately 11 cm3 containing, in order, absorbent for carbon dioxide (4.34), and magnesium perchlorate (4.20), fixed in place with cotton wool plugs 9 bubble counter, containing concentrated sulfuric acid (4.13) 10 vacuum Figure 1 – Apparatus for TOC determination by wet oxidation method WARNING — Use of acid resistant fume cupboards and acid resistant gloves is obligatory 6.3 Procedure Weigh, to an accuracy of ± 0,000 5 g, (1,00 ± 0,05) g of limestone (m1). Transfer to the 150 ml round flask, add 2 ml of water and 30 ml of phosphoric acid (4.12). Heat the mixture and boil gently for 4 min to expel the carbon dioxide. Cool the mixture and connect the flask to the apparatus. Substitute for the absorption tube (see Figure 1, no. 8) a glass tube and pass 2 I of carrier gas (4.6) through the apparatus to clear the system of any carbon dioxide. Fit the weighed absorption tube again to the apparatus and SIST EN 13639:2017

is the mass of the absorption tube before absorption of carbon dioxide in grams; mu2 is the mass of the absorption tube after absorption of carbon dioxide in grams; m1 is the mass of the sample in grams. 7 Gravimetric method with furnace oxidation (alternative method No. 1) 7.1 Principle The carbon dioxide in the limestone is driven off by use of hydrochloric acid (4.9) at approximately 130 °C. The insolubl
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