1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationPD CEN/TS 16375:2013Liming materials Determination of the amountof residual finely groundcarbonate in soils VolumetricmethodPD CEN/TS 16375:2013 PUBLISHED DOCUMENTNational forewo
2、rdThis Published Document is the UK implementation ofCEN/TS 16375:2013.The UK participation in its preparation was entrusted to TechnicalCommittee CII/37, Fertilisers and related chemicals.A list of organizations represented on this committee can beobtained on request to its secretary.This publicati
3、on does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2013. Published by BSI StandardsLimited 2013 ISBN 978 0 580 75378 7 ICS 65.080 Compliance with a British Standard cannot confer immunity froml
4、egal obligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 31 January 2013. Amendments issued since publicationDate T e x t a f f e c t e dPD CEN/TS 16375:2013TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/
5、TS 16375 January 2013 ICS 65.080 English Version Liming materials - Determination of the amount of residual finely ground carbonate in soils - Volumetric method Amendements minraux basiques - Dtermination de la teneur en carbonate rsiduel finement broy dans les sols -Mthode volumtrique Calcium-/Magn
6、esium-Bodenverbesserungsmittel - Bestimmung der Menge feingemahlener Carbonatrckstnde in Bden - Volumetrisches VerfahrenThis Technical Specification (CEN/TS) was approved by CEN on 27 May 2012 for provisional application. The period of validity of this CEN/TS is limited initially to three years. Aft
7、er two years the members of CEN will be requested to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promp
8、tly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, B
9、ulgaria, 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, Slovakia, Slovenia, Spain, Sweden, Switzerland,
10、 Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No.
11、 CEN/TS 16375:2013: EPD CEN/TS 16375:2013CEN/TS 16375:2013 (E) 2 Contents Page Foreword . 3 1 Scope 4 2 Normative references . 4 3 Principle 4 4 Reagents . 4 5 Apparatus . 4 6 Procedure . 7 6.1 Preparation of the apparatus . 7 6.2 Sample preparation 8 6.3 Measurement procedure 8 7 Method by controll
12、ed additions . 9 7.1 General . 9 7.2 Procedure . 9 7.3 Calculation and expression of the results 9 8 Method by direct measurement . 10 8.1 General . 10 8.2 Choice of a pilot soil without carbonate . 10 8.3 Calibration of the calcimeter 10 8.3.1 Procedure . 10 8.3.2 Calculation and expression of the
13、result 10 8.4 Measurement of an unknown sample . 11 8.4.1 Procedure . 11 8.4.2 Calculation and expression of the results 11 9 Precision . 11 9.1 Inter-laboratory test . 11 9.2 Repeatability . 12 9.3 Reproducibility . 12 10 Test report 13 Annex A (informative) Using spread sheet software to calculate
14、 linear regression 14 Bibliography 15 PD CEN/TS 16375:2013CEN/TS 16375:2013 (E) 3 Foreword This document (CEN/TS 16375:2013) has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming materials”, the secretariat of which is held by DIN. Attention is drawn to the possibility that som
15、e of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following countries are bound to anno
16、unce this Technical Specification: 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, Ro
17、mania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. PD CEN/TS 16375:2013CEN/TS 16375:2013 (E) 4 1 Scope This Technical Specification specifies a method for the determination of low contents (as 5 g CaCO3per kilogram) of carbonate in soil samples. It applies to any t
18、ype of carbonate liming material, such as limestone, chalk, and dolomite. 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 refe
19、rences, the latest edition of the referenced document (including any amendments) applies. EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696) 3 Principle Hydrochloric acid is added to a soil sample to decompose any carbonates present. The reaction in simplified
20、 form reads as follows (Me means metal): 3223COHMe2HMeCO +2232COOHCOH + (gaseous) The volume of the carbon dioxide produced is measured with a measuring burette, and is compared with the volume of gas produced by increasing amounts of calcium carbonate added to test portions. To avoid making correct
21、ions for differences in temperature and pressure, all determinations are carried out under the same conditions, with a very strict control of ambient conditions and determination timing, e.g. air-conditioned room and water bath, short time during which the variation of atmospheric pressure is suppos
22、ed to be constant. 4 Reagents Use only reagents of recognized analytical grade. 4.1 Water, with a specific electrical conductivity not higher than 0,2 mS/m at 25 C (conforming to grade 2 of EN ISO 3696). 4.2 Hydrochloric acid, c(HCl) = 4 mol/l. Dilute 340 ml of 37 % hydrochloric acid in water (4.1)
23、and then fill up to 1 000 ml with water (4.1). 4.3 Sulfuric acid, (H2SO4) solution 95 % to 97 %. 4.4 Sodium sulfate, (Na2SO4), powder, purity higher than 99 %. 4.5 Internal liquid of the calcimeter, 50 g/l of sodium sulfate (4.4) and 50 ml/l of sulfuric acid (4.3). 4.6 Calcium carbonate, (CaCO3), po
24、wder, purity higher than 99 %. 5 Apparatus 5.1 Apparatus for the volumetric measurement of produced gas, inspired of Bernard calcimeter according to Figure 1. The apparatus is composed of a glass tube of 20 ml graduated every 0,02 ml. The total length shall not exceed 80 cm. Another non graduated gl
25、ass tube with the same length and the same diameter is connected to the first glass tube with a transparent flexible pipe of about 1 m. A small volume of reserve of 50 ml can be inserted right at the inferior end of the graduated tube. The higher end of the graduated tube is connected by a standard
26、flexible pipe to the Erlenmeyer flask (5.2) of attack. PD CEN/TS 16375:2013CEN/TS 16375:2013 (E) 5 The graduated tube is fixed vertically on a stand. The non-graduated tube is held on a second stand, parallel to the first, but so that it is vertically mobile. Mark the tube to approximately 2 cm of i
27、ts lower end. The two tubes shall only be 1 mm or 2 mm away from each other. The whole apparatus shall be dipped several hours in a surface-active cleaning liquid to eliminate any trace on the interior surface of the tubes which could hinder circulation and modify the levelling of the internal liqui
28、d. Rinse with demineralised water after treatment. PD CEN/TS 16375:2013CEN/TS 16375:2013 (E) 6 Key A glass tube of 20 ml graduated every 0,02 ml B non-graduated tube C flexible pipe C standard flexible pipe D bulb of 50 ml E 200 ml Erlenmeyer flask with finely ground, gas tight glass stopper F water
29、 bath L metallic ring R 3 ways tap S stand T reaction tube (with hydrochloric acid) Figure 1 Calcimeter 5.2 200 ml Erlenmeyer flask, with finely ground, gas tight glass stopper. Erlenmeyer flasks of attack, with a capacity of 200 ml, are closed by a finely ground glass cup. The upper part of the cap
30、 is connected by 200 mm of standard flexible pipe to a 3 ways tap of polytetrafluoroethylene, PTFE), which is also connected to the flexible pipe coming from the graduated tube. The waterproof of the glass cap is ensured by a thin silicone-grease layer. 5.3 Water bath, the volume of water shall be o
31、f at least 5 l and maintain at room temperature. PD CEN/TS 16375:2013CEN/TS 16375:2013 (E) 7 5.4 Metallic ring. The Erlenmeyer flask of attack (5.2) is ballasted with a metallic ring and is kept in the water bath. 5.5 Thermo stated room. The whole device is placed in a thermo stated room of a great
32、thermal inertia or fit with a device of cold-hot regulation which ensures an uninterrupted constant temperature to 1 C. Check the room temperature changes close to the device for 1 h. The analysis may only start when the water bath temperature is equal to the room temperature. Absence of important a
33、tmospheric pressure variation during the analysis shall be checked to the regional weather services. 5.6 Glass tubes, capacity of 20 ml. Each tube shall have a length such to allow that: it can be vertically introduced into the Erlenmeyer flask using a finger, it can be maintained in sub-vertical po
34、sition in the Erlenmeyer flask without its contents pours out, its contents can be completely emptied in the Erlenmeyer flask by inclining the Erlenmeyer flask at an angle lower than 90. 5.7 Thermometer, with an accuracy of 0,2 C. 5.8 Analytical balance, with an accuracy of 0,01 mg. 5.9 Stop watch.
35、6 Procedure 6.1 Preparation of the apparatus 6.1.1 Fill the apparatus with the internal liquid (4.5). Use a small funnel connected by a flexible pipe at the higher end of the non-graduated tube. Eliminate air bubbles. 6.1.2 Fill the tube until the liquid level match with the first higher graduation
36、(position zero) of the graduated tube and the mark traced in the lower part of the non-graduated tube. 6.1.3 Make sure that the two meniscuses positions are on the same horizontal level (the apparatus is not connected to the Erlenmeyer flask at this point). 6.1.4 Make the non-graduated tube slide do
37、wnwards. The volume of liquid then goes down the graduated tube. Check, in several points of volume, the horizontal coincidence of the meniscuses. 6.1.5 Reset the meniscuses to position zero. 6.1.6 Lay the water bath close to the device. 6.1.7 Let the whole device stabilize thermically for 0,5 h. 6.
38、1.8 Check that the water bath temperature is equal to the room temperature. PD CEN/TS 16375:2013CEN/TS 16375:2013 (E) 8 6.2 Sample preparation NOTE Particular care is necessary to prepare the sample. 6.2.1 The minimum amount of the sample for the laboratory shall be 500 g. 6.2.2 Reduce all of the sa
39、mples taken up to 2 mm, avoiding producing too many fine particles. A pestle and mortar should be used because they are undoubtedly the best system of crushing. 6.2.3 Use a sieve with a pore size of 2 mm. 6.2.4 Introduce the fine soil into a polyethylene flask. Leave an empty volume that shall be at
40、 least half of the flask. Stir upside down at 40 min-1for 2 h. 6.2.5 Recover the whole sample or a part of the sample prepared in this way for the weighing of test portions. 6.3 Measurement procedure 6.3.1 The reagents used (4.1 and 4.2) shall be at room temperature. 6.3.2 Add to the Erlenmeyer flas
41、k (5.2) containing the test portion, 10 ml of water (4.1). Mix gently for 30 s. 6.3.3 Pour carefully in a glass tube (5.6) 10 ml of hydrochloric acid (4.2). Avoid any contamination of the acid outside the tube. 6.3.4 Introduce the tube vertically into the Erlenmeyer flask (5.2), by avoiding any disc
42、harge or splashes of acid outside the tube. 6.3.5 Place the Erlenmeyer flask in the water bath by ballasting it with a metallic ring (5.4). 6.3.6 Start the stopwatch (5.9), (t = 0). 6.3.7 Connect the Erlenmeyer flask (5.2) to the calcimeter with a finely ground, gas tight glass stopper slightly lubr
43、icated. Open and close the tap to connect the Erlenmeyer flask and the graduated tube. 6.3.8 Check that the meniscus shows the position zero, if not open and close the tap. 6.3.9 At time t = 1 min, keep the Erlenmeyer flask at the top of the water bath and pour the acid contained in the tube as quic
44、kly as possible, by inclining the Erlenmeyer flask. Shake by hand, with a circular movement for 30 s. 6.3.10 During this operation, the Erlenmeyer flask shall be handled by the neck not to transfer heat from the hands (use a fabric or a glove). 6.3.11 Plunge the Erlenmeyer flask in the water bath ag
45、ain. 6.3.12 Make the tube that is not graduated slide downwards to adjust the two meniscuses to the same level. 6.3.13 At time t = 3 min, shake the Erlenmeyer flask again as before for 30 s and plunge it again in the water bath. 6.3.14 At time t = 6 min, make coincide meniscuses on the same horizont
46、al level and read the volume of released CO2to the nearest 0,02 ml. 6.3.15 If combined magnesium and calcium is expected, read the volume at 20 min. Shake for 30 s every 5 min (for instance: at 8 min, 13 min, 18 min). PD CEN/TS 16375:2013CEN/TS 16375:2013 (E) 9 7 Method by controlled additions 7.1 G
47、eneral This method is to be used when a sample of soil containing carbonate is not available. 7.2 Procedure 7.2.1 Weigh 5 g, 10 g and 20 g of sample to the nearest 0,001 g in three different Erlenmeyer flasks. Let the Erlenmeyer flasks stabilize thermically close to the calcimeter. 7.2.2 Begin measu
48、rement with the weakest test portion. Determine test portion, m, which corresponds to an awaited gas release from approximately 2 ml to 3 ml without going down lower than 2 g. 7.2.3 Weigh in three different Erlenmeyer flasks the same test portion, m. 7.2.4 In the second Erlenmeyer flask, add approxi
49、mately 15 mg of powder CaCO3(4.6). 7.2.5 In the third Erlenmeyer flask, add approximately 30 mg of powder CaCO3(4.6). 7.2.6 Record the exact added weights to 0,01 mg. 7.2.7 Mix CaCO3with the soil of the test portion and carry out measurements as indicated in 6.3. 7.3 Calculation and expression of the results Determine by linear regression the relation of calibration between the degassed volume of CO2and the amount of CaCO3. Determine the measured volume of CO2, y(1), in millilitre, by linear regression according to Formula (1). baxy +=)1(1) where
