1、BSI Standards PublicationBS ISO 22016:2015Determination of sulfur inrefractory products and rawmaterials by gravimetric,photometric and titrimetricmethodsBS ISO 22016:2015 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 22016:2015.The UK participation in its pr
2、eparation was entrusted to TechnicalCommittee RPI/1, Refractory products and materials.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for it
3、s correctapplication. The British Standards Institution 2015. Published by BSI StandardsLimited 2015ISBN 978 0 580 81673 4ICS 81.080Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strat
4、egy Committee on 31 May 2015.Amendments issued since publicationDate Text affectedBS ISO 22016:2015 ISO 2015Determination of sulfur in refractory products and raw materials by gravimetric, photometric and titrimetric methodsDosage du soufre dans les produits rfractaires et les matriaux bruts par gra
5、vimtrie, et des mthodes photomtriques et titrimtriquesINTERNATIONAL STANDARDISO22016First edition2015-05-15Reference numberISO 22016:2015(E)BS ISO 22016:2015ISO 22016:2015(E)ii ISO 2015 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2015, Published in SwitzerlandAll rights reserved. Unless othe
6、rwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address
7、below or ISOs member body in the country of the requester.ISO copyright officeCh. de Blandonnet 8 CP 401CH-1214 Vernier, Geneva, SwitzerlandTel. +41 22 749 01 11Fax +41 22 749 09 47copyrightiso.orgwww.iso.orgBS ISO 22016:2015ISO 22016:2015(E)Foreword iv1 Scope . 12 Normative references 13 Terms and
8、definitions . 14 Apparatus . 14.1 General . 14.2 Apparatus specified in method B 25 Reagents 35.1 General . 35.2 Standard solutions for method B 56 Sample preparation . 57 Determination of sulfur 67.1 General . 67.2 Method A 67.2.1 Method A1 . 67.2.2 Method A2 . 77.3 Method B 87.3.1 Principle 87.3.2
9、 Mass of test portion . 87.3.3 Procedure . 87.3.4 Blank test 97.3.5 Calculation . 97.4 Method C 97.4.1 Principle 97.4.2 Mass of test portion . 97.4.3 Procedure . 97.4.4 Calculation 108 Test report 10Annex A (informative) Statistical results of sulfur analyses in refractories and raw materials 11Bibl
10、iography .13 ISO 2015 All rights reserved iiiContents PageBS ISO 22016:2015ISO 22016:2015(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried o
11、ut through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO c
12、ollaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different app
13、roval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).Attention is drawn to the possibility that some of the elements of this document may be the
14、subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development of the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents).Any t
15、rade name used in this document is information given for the convenience of users and does not constitute an endorsement.For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the
16、Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information.The committee responsible for this document is ISO/TC 33, Refractories.iv ISO 2015 All rights reservedBS ISO 22016:2015Determination of sulfur in refractory products and raw materials by gravimetric, photom
17、etric and titrimetric methods1 ScopeThis International Standard specifies methods for the wet chemical analysis of refractory products and their raw materials with below 5 % (mass percentage) sulfur.2 Normative referencesThe following documents, in whole or in part, are normatively referenced in thi
18、s 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 any amendments) applies.ISO 836, Terminology for refractoriesISO 6353-1, Reagents for chemical analysis Part 1:
19、 General test methodsISO 6353-2, Reagents for chemical analysis Part 2: Specifications First seriesISO 6353-3, Reagents for chemical analysis Part 3: Specifications Second seriesISO 8656-1, Refractory products Sampling of raw materials and unshaped products Part 1: Sampling schemeISO 26845, Chemical
20、 analysis of refractories General requirements for wet chemical analysis, atomic absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) methods3 Terms and definitionsFor the purposes of this document, the terms and definitions given in ISO 836, ISO 26845,
21、 and the following apply.3.1sulfurgeneral term for elemental sulfur, sulfides, sulfates, sulfites, etc. in refractory products and their raw materials4 Apparatus4.1 GeneralThe following apparatus is required in addition to ordinary laboratory apparatus and the apparatus given in ISO 26845.4.1.1 Plat
22、inum crucible, with a nominal volume of 25 ml, made, for example, in Pt/Au 95/5 %.4.1.2 pH-meter.4.1.3 Electrically heated furnace, adjustable to (1 150 25) C.INTERNATIONAL STANDARD ISO 22016:2015(E) ISO 2015 All rights reserved 1BS ISO 22016:2015ISO 22016:2015(E)4.2 Apparatus specified in method B4
23、.2.1 Apparatus for tin(II): strong phosphoric acid solution preparation, an example of an apparatus consisting of a quartz flask is shown in Figure 1.Key1 thermometer (360 C) 5 cap made of quartz2 quartz tubes ( 10 mm) 6 quartz flask (500 ml)3 tap aspirator 7 quartz tube ( 10 mm)4 N2 gas 8 heating m
24、antleFigure 1 Example of apparatus for tin(II): strong phosphoric acid solution preparation4.2.2 Sample decomposition and gas absorption equipment, example of apparatus is shown in Figure 2.2 ISO 2015 All rights reservedBS ISO 22016:2015ISO 22016:2015(E)Key1 thermometer 0 C to 310 C 6 test tube for
25、absorption ( 30 mm)2 quartz tube 7 glass tube for absorption3 N2gas 8 zinc acetate solution4 polyethylene tetrafluoride resin connecting tube 9 aluminium foil wall5 test tube for decomposition ( 30 mm) 10 heater (300 W)Figure 2 Example of sample decomposition and gas absorption equipment5 Reagents5.
26、1 GeneralPrepare the following reagents and those given in ISO 26845, as necessary.Use only reagents of recognized analytical grade during the analysis unless otherwise stated and only distilled water or water of equivalent purity.Reagents should conform to the requirements of ISO 6353-1, ISO 6353-2
27、, and ISO 6353-3, as appropriate.5.1.1 Silver nitrate solution (10 g/l), dissolve 1 g of silver nitrate into 100 ml of water. Store the solution in an amber-coloured bottle.5.1.2 Sodium carbonate solution (5 g/l), dissolve 5 g of anhydrous sodium carbonate into 1 l of water.5.1.3 Sodium thiosulfate
28、pentahydrate for Method B, Na2S2O35H2O, (ISO 6353-2, R 36), minimum mass fraction 99,0 %.5.1.4 Potassium nitrate.5.1.5 Barium chloride di-hydrate for Method A2, BaCl22H2O. ISO 2015 All rights reserved 3BS ISO 22016:2015ISO 22016:2015(E)5.1.6 Barium chloride solution.5.1.6.1 100 g/l anhydrous BaCl2fo
29、r Method A1, 10 g of anhydrous barium chloride is dissolved in water and made up 100 ml.5.1.6.2 100 g/l BaCl22H2O for Method A2, 10,0 g Barium chloride di-hydrate (5.1.5) is dissolved in water and made up to 100 ml.5.1.6.3 5,42 g/l anhydrous BaCl2for Method C, 0,542 g of anhydrous barium chloride is
30、 dissolved in water and made up to 100 ml.5.1.7 Tin(II): strong phosphoric acid solution for Method B, transfer 500 g of phosphoric acid into the quartz flask in Figure 1 in Clause 5, heat it to 250 C for 1 h to dehydrate, draw with water aspirator to remove steam generated, and cool. Add 80 g of an
31、hydrous tin(II) chloride, heat the mixture under nitrogen gas to 300 C, cool to room temperature under nitrogen gas, and store in a desiccator.5.1.8 Zinc acetate solution for Method B, dissolve 40 g of anhydrous zinc acetate into approximately 300 ml of water, add 30 ml of acetic acid to the solutio
32、n, dilute to 1 000 ml with water, and store in a plastic bottle.5.1.9 Starch solution for Method B, dissolve 0,1 g of starch (soluble) into approximately 10 ml of water, add this solution into 200 ml of hot water (80 C 10 C) while agitating, boil for about 1 min and cool to room temperature, store i
33、n a cold place, and discard after 10 days.5.1.10 Sulfate solution, S 0,1mg/ml, dry about 1 g of sodium sulfate, Na2SO4, at 110 C 5 C for 2 h. Dissolve 0,443 g in water, diluting to 1 000 ml in a volumetric flask.5.1.11 Potassium iodate, KIO3, reference material for volumetric analysis or reagent of
34、at least mass fraction 99,95 % purity.5.1.12 Potassium iodide, KI, (ISO 6353-2, R 25), minimum mass fraction 99,5 %.5.1.13 Iodine solution for Method B, 0,01 mol/l, weigh 1,27 g of iodine and 10 g of potassium iodide (5.1.12) and dissolve in approximately 50 ml of water, diluting to 1 000 ml in a vo
35、lumetric flask. Store the solution in an amber-coloured bottle.5.1.14 Mixture acid for Method C, hydrochloric acid (concentrated) and nitric acid (V) (concentrated) in a ratio of 3:1, prepared before use.5.1.15 Ammonia solution, concentrated, = 0,91 g/ml and 1+1 solution for method C.5.1.16 EDTA aci
36、d ammonium salt solution for Method C, dissolve 10 g of EDTA in 200 ml of water, add 100 ml of ammonia (concentrated), and dilute to 500 ml with water.5.1.17 Sodium carbonate/potassium carbonate mixture for Method A2, one part Na2CO3and one part K2CO3are well mixed.5.1.18 Potassium nitrate, KNO3.5.1
37、.19 Hydrochloric acid, HCl 6 mol/l, supplied as 6M or dilute 530 ml of conc. HCl (SG 1.18) to 1 l in water4 ISO 2015 All rights reservedBS ISO 22016:2015ISO 22016:2015(E)5.1.20 Hydrochloric acid, HCl 2 mol/l, supplied as 2M or dilute one part of hydrochloric acid (5.1.9) with two parts of water.5.1.
38、21 Hydrofluoric acid, HF, w(HF) = 40 %, = 1,13 g/ml.5.2 Standard solutions for method B5.2.1 0,01 mol/l sodium thiosulfate standard solution, weigh 2,6 g of sodium thiosulfate pentahydrate (5.1.3) and 0,2 g of sodium carbonate, dissolve in 1 l of dissolved oxygen-free water. Store the solution in an
39、 airtight container. Let it stand for 2 days prior to use.5.2.1.1 StandardizationDry 0,5 g of potassium iodate (5.1.11) at 130 C for 2 h and allow it to cool in a desiccator. Weigh 0,3 g to 0,4 g to the nearest 0,1 mg and dissolve in water, diluting to 1 000 ml in a volumetric flask. Pipette 25 ml i
40、nto a 200 ml Erlenmeyer flask, add 2 g of potassium iodide (5.1.12), and 2 ml of sulfuric acid (1+1), immediately stopper the flask, shake gently for 1 min, and allow it to stand for 5 min in a dark place. Add starch solution and titrate with the 0,01 mol/l sodium thiosulfate standard solution until
41、 it becomes faint yellow which shows the end point is near. Complete disappearance of blue colour indicates the end point.Separately, add 25 ml of water and 2 g of potassium iodide into a 200 ml Erlenmeyer flask, add 2 ml of sulfuric acid (1+1), immediately stopper the flask, shake gently, and allow
42、 it to stand for 5 min in a dark place. Carry out a blank test under the same conditions as above and correct the volume needed for titration.5.2.1.2 CalculationCalculate the factor according to Formula (1):fmvva=25 1 0000 000 356 67 10012/,()(1)wheref is the factor of 0,01 mol/l sodium thiosulfate
43、standard solution;m is the mass of potassium iodate weighed out, in g;a is the purity of potassium iodate, in %;0,000 356 67 is the mass of potassium iodate equivalent to 1 ml of 0,01 mol/l sodium thiosulfate standard solution, in g;v1is the volume of 0,01 mol/l sodium thiosulfate standard solution
44、needed for titra-tion of potassium iodate, in ml;v2is the volume of 0,01 mol/l sodium thiosulfate standard solution needed for titra-tion of blank test, in ml.6 Sample preparationThe sampling shall be conducted according to ISO 8656-1 or as agreed upon between the parties involved. The sample shall
45、be dried at (110 + 5) C to constant weight. If necessary, any agglomerated material shall be ground and homogenised. ISO 2015 All rights reserved 5BS ISO 22016:2015ISO 22016:2015(E)7 Determination of sulfur7.1 GeneralThe determination of sulfur is carried out using one of the following methods. Meth
46、od A: Fusion with alkali carbonate - barium sulfate gravimetric method. This method is applied to samples with 0,01% to 5% sulfur percentage (mass percentage). Method B: Decomposition by tin(II) - strong phosphoric acid solution - Iodine and thiosulfate back-titration method. This method is applied
47、to samples with below 0,1% sulfur percentage (mass percentage). Method C: Barium sulfate (VI) precipitated by oxidation is determined by flame photometry. This method is applied to samples up to 5% sulfur percentage (mass percentage).7.2 Method ANOTE The sulfur analytical procedures for the gravimet
48、ric method are described individually although they are based on the same principle and subdivided into methods A1 and A2.7.2.1 Method A17.2.1.1 PrincipleSodium carbonate and potassium nitrate are added to a sample and the mixture is fused by heating in an electric furnace. The sulfur contained in t
49、he sample is stabilised as alkali sulfate. The fused salts are dissolved with water and the resulting solution is filtered to separate the insoluble matter. Ethanol and hydrochloric acid are added to the filtrate and heated in order to reduce chromium (VI) oxide and to remove carbon dioxide from the decomposition of sodium carbonate. Barium chloride solution is added into the resulting solution to precipitate sulfur in the form of barium sulfate. The precipitate is filtered and calcined and t
