Common Market for Eastern and Southern Africa ≠ EDICT OF GOVERNMENT ± In order to promote public education and public safety, equal justice for all, a better informed citizenry, the rule of law, world trade and world peace, this legal document is hereby made available on a noncommercial basis, as it is the right of all humans to know and speak the laws that govern them. COMESA 241 (2006) (English): Surface-active agents and detergents - Determination of water content - Karl Fischer method COMESA HARMONISED COMESA/DHS STANDARD 241:2005 Surface-active agents and detergents - Determination of water content - Karl Fischer method REFERENCE: DHS 241: 2005 Foreword The Common Market for Eastern and Southern Africa (COMESA) was established in 1994 as a regional economic grouping consisting of 20 member states after signing the co-operation Treaty. In Chapter 15 of the COMESA Treaty, Member States agreed to co-operate on matters of standardisation and Quality assurance with the aim of facilitating the faster movement of goods and services within the region so as to enhance expansion of intra-COMESA trade and industrial expansion. Co-operation in standardisation is expected to result into having uniformly harmonised standards. Harmonisation of standards within the region is expected to reduce Technical Barriers to Trade that are normally encountered when goods and services are exchanged between COMESA Member States due to differences in technical requirements. Harmonized COMESA Standards are also expected to result into benefits such as greater industrial productivity and competitiveness, increased agricultural production and food security, a more rational exploitation of natural resources among others. COMESA Standards are developed by the COMESA experts on standards representing the National Standards Bodies and other stakeholders within the region in accordance with international procedures and practices. Standards are approved by circulating Final Draft Harmonized Standards (FDHS) to all member states for a one Month vote. The assumption is that all contentious issues would have been resolved during the previous stages or that an international or regional standard being adopted has been subjected through a development process consistent with accepted international practice. COMESA Standards are subject to review, to keep pace with technological advances. Users of the COMESA Harmonized Standards are therefore expected to ensure that they always have the latest version of the standards they are implementing. This COMESA standard is technically identical to ISO 4317; 1991, Surface-active agents and Detergents -Determination of water content - Karl Fischer method A COMESA Harmonized Standard does not purport to include all necessary provisions of a contract. Users are responsible for its correct application. INTERNATIONAL STANDARD Second edition 1991-08-01 ----- w _--- Surface-active agents and detergents ‘- Determination of water content - Karl Fischer method Agents de sur-face et detergents - D6terminafion de la teneur en . eau - Methode de Karl Fischer PP ~------ --- - -- - Refw-ence number ISC) 4317:1991(E) ISO 4317:1991(E) Foreword ISO (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 out through ISO technical committees. Esch 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, govern- mental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an lnter- national Standard requires approval by at least 75 % of the member bodies casting a vote. International Standard ISO 4317 was prepared by Technical Committee ISO/TC 91, Surface active agents. This second edition cancels and replaces the lit-st edition (ISO 4317:1977), of which it constitutes a technical revision. Annexes A and B of this International Standard are for information only. 0 ISO 1991 All rights reserved. No part of this publication may be reproduced or utilized in any form or by any means, electronie or mechanical, including photocopying and microfilm, without Permission in writing from the publisher. International Organization for Stand ardiz ation Case Postale 56 l CH-121 1 Geneve 20 l Switzeriand Printed in Switzerland ii INTERNATIONAL STANDARD ISO 4317:1991 (E) Surface-active agents and detergents - Determination of water content - Karl Fischer method 1 Scope ISO 3696:1987, Water for analyfical laboratory use - Specification and test methods. This International Standard specifies a method using Karl Fischer reagent for the determination of the 3 Definition water content of surface-active agents and deter- gents. For the purposes of this International Standard, the The method is applicable to products in the form of following definition applies. powders, pastes and solutions. For water contents of less than 1 % (174174, it is the only method to be 3.1 water content: The amount of free water, water used. of crystallization, absorbed water or occluded water, expressed as a percentage by mass, calculated lt is applicable only if so indicated in the specific from the amount of Karl Fischer reagent used in ac- Standard for each product. cordante with this International Standard. As alkaline compounds react with Karl Fischer re- agent, the method gives too high values in the case 4 Principle of samples containing alkali metal silicates, carbon- ates, hydroxides or borates. Therefore, samples Any water present in a test portion is reacted with shall be analysed for the presence of such alkali a Solution of iodine and Sulfur dioxidlz in an appro- metal salts Prior to the determination of the water priate mixture (Karl Fischer. reagent), previously content. standardized by titration with an exactly known mass of water. The water content is calculatecl as a NOTE 1 A summary of a coulometric method is q\ iven in percentage by mass from the amount of reagent annex B for information. used. 5 Reagents 2 Normative references During the analysis, use only reagents of recognized The following Standards contain provisions which, analytical grade and only grade 2 distilled water through reference in this text, constitute provisions (5.1). of this International Standard. At the time of publi- cation, the editions indicated were valid. All stan- dards are subject to revision, and Parties to 5.1 Distilled water, or water of at least equivalent agreements based on this International Standard purity, complying with the requirements of ISO 3696 are encouraged to investigate the possibility of ap- for grade 2. plying the most recent editions of the Standards in- dicated below. Members of IEC and ISO maintain 5.2 Methanol, dry. registers of currently valid International Standards. ISO 607:1980, Surface active agents and detergents 5.3 Karl Fischer reagent, preferably commercially - Methods of Sample division. prepared. ISO 760:1978, Determination of water - Karl Fischer NOTE 2 A reagent containing pyridine may be prepared method (General method). as described in annex A for information. ISO 4317:1991 (E) A non-pyridine reagent tan be used if it has been 6.5 One-mark volumetric flask, capacity 100 ml. shown to be suitable (to be included in the test re- P0r-W NOTE 3 A suitable non-pyridine-containing reagent is commercially availabfe containing iodine, Sulfur dioxide and an amine dissolved in 2-methoxyethanol. 7 Sampling 5.4 Disodium tartrate dihydrate or oxalic acid The Iaboratory Sample of surface-active agent or dihydrate, to be used as the primary Standard for the detergent shall have been prepared and stored in Karl Fischer reagent, or water (5.1). accordance with the instructions given in 133 607. 5.5 Solvent, e.g. 2-methoxyethanol, propan-1-01 or methanol. If it is known that these solvents interfere with the determination, e-g. for the determination of water in 8 Procedure aldehydes or ketones, trichloromethane or dichloromethane may be used (if so, this shall be Atrnospheric moisture is the biggest sourc:e of in- indicated in the test report). terference in the Karl Fischer titration. Special at- ten.tion shall be paid to thorough drying of the WARNING - Trichloromethane and dichloromethane apparatus used and speedy handling of the test are harmful by inhalation and if swallowed, and irri- portions and solvents. For the method of use of the tating to the skin, with the risk of irreversible effects Karl Fischer apparatus, follow the manufacturer’s and the danger of serious damaqme to health in the instructions and ISO 760. event of prolonged exposure. 8.1 Determination of the water equivalent of fke Karl Fischer reagent (5.3) Determine the water equivalent of the reagent on each new Container of reagent and then at least 6 Apparatus weekly. Ordinary laboratory apparatus and, in particular: It is necessary to check the titre of the Karl Fischer reagent, as the titre of the Standard solvtions is 6.1 Karl Fischer apparatus, fully automatic or subject to Change. The type of apparatus used and semi-automatic, consisting of: the desired analytical accuracy g. overn the fre- guency of such titre Checks. - titrator with double platinum electrode; Place the magnetic stirrinq bar into the titration - 20 ml Piston burette; vessel of the Karl Fischer apparatus (6A) using pincers, and transfer IO ml of one of the solvents - drying tubes containing activated silica gel, (5.5) used for the determination into the titration Calcium chloride or magnesium perchlorate; vessel and titrate with the Karl Fischer reagent (S.3). - titration vessel; In cases where it is absolutely necessary, e.g. the - magnetic stirring apparatus. determination of water in aldehydes or ketones, use chloroform or dichloromethane (see 5.5) as solvent. 6.2 Micrometer Syringe, capacity 100 ~1. t7fh er: 6.3 Graduated pipette, capacity 20 ml. Weiyh 200 mg to 250 mg of disodium tartrate dihydrate or oxalic acid dihydrate (5.4) in a weighing 6.4 Syringe, nominal capacity about IO ml, with a scoop to the nearest 0,l mg. Transfer the tartrate or glass tube with an internal diameter of 2 mm to oxalic acid to the titration vessel and reweigh the 4 mm, with a movable needle attached to the weighing SCOOP. Dissolve the lartrate or oxalic acid Syringe by suitable means. in the solvent by gentle stirring. ISO 4317:1991 (E) oc By means of the graduated pipette (6.3), take a vol- ume of the supernatant methanoliv’ Solution corre- Introduce approximately 40 mg of water (5.1) from a sponding to 10 mg to 50 mg of water. dropping bottle, weighed before and after introduc- ing the watcr into the titration vessel. NOTE 4 For some surface-active agents, for example zeolites, only part of the water of crystallization will be The amount of solvent used shall be such as to im- determined by the method described. merse the electrode by 2 mm to 3 mm. 8.3 Determination of the water content Add Karl Fischer reagent until the electrometric end Point has been reached. This is when, afler addition Place 20 ml of solvent (5.5) and the magnetic stirring of Karl Fischer reagent drop by drop, the observed bar (using pincers) in the titration vessel of the Karl value remains constant for 30 s. Fischer apparatus (6.1). Whilst stirring, add Karl The watet- equivalent p(H@), expressed in milli- Fischer reagent (5.3) until the end Point is reached grams of water per millilitre, is given by one of the as indicated by the instrument reading. DO not re- following equations: Cord the amount of reagent used. n?,-w(H,O) Add the test portion (see 8.2). Stir to dissolve, and Pw,O) =I titrate to the Same end Point. Record the volume of IOOV, Karl Fischer reagent used. Carry out a second determination by addinq another test Portion and repeating the titration. ’ m2 dH,O)=y- 1 where 9 Expression of resuits is the mass, in milligrams, of disodium The water content of the product, expressed as a tartrate dihydrate or oxalic acid percentaqe. by mass, is qLi ven byI the formula: dihydrate (5.4) used; Pw2w% x IO0 j*2 is the mass, in milligrams, of water mo (5.1) used; w(H,O) is the water content, expressed as a v percentage by mass, of the primary is the volume, in millilitres, of Karl 2 Standard (5.4) used, i.e. 15,66 for Fischer reagent (5.3) used for the de- sodium tartrate dihydrate or 28,57 for termination (see 8.3); oxalic acid dihydrate; is the mass, in milligrams, of the test K is the volume, in millilitres, of Karl portion (see 8.2); Fischer reagent 5.3) used in the p(H,O) is as defined in 8.1. titration. 8.2 Test Portion 10 Precision If the Sample has a water content less than 1 % (m/m), use 5 g to 10 g (preferably to contain 10.1 Repeatability 10 mg to 50 mg water) of the laboratory Sample (see clause 7), weighed to the nearest 1 mg. The differente between the results of two determi- nations carried out simultaneously 01’ in rapid suc- If the sam ple has a wate r content higher than cession by the Same Operator on the Same Sample 1 % (nz/rn) , prepare the test Portion as foIlows: should not be greater than 6 O/or elatiw. Weigh, to the nearest 1 mg, 1 g to 5 g of the labora- tory Sample into the 100 ml volumetric flask (6.5). 10.2 Reproducibility Add dry methanol (5.2) and dilute to the mark. Dis- solve the water present in the Sample by vigorous The differente between two results cbtained in dif- shaking. Insoluble salts will settle to the bottom ferent laboratories on portions of the Same Sample when the Solution is allowed to stand. should not be greater than 10 % relative. ISO 4317:1991 (E) 11 Test report c) the results obtained and the units in which they have been expressed; The test report shall include the following partic- ulars: d) the test conditions; a) all information necessary for the complete iden- e) any operational details not specified in this In- tification of the Sample; ternational Standard or in the International Stan- dards to which reference is made, as weil as any b) a reference to this International Standard and the operational details regarded as optional, plus type of solvent and of Karl Fischer reagent used; details of any incidents Iikely to have affected the results.