17 tS) (@3 ANALYTICAL CHEMISTRY NN hes Dinindai denaan CamScannerBasic Analytical Chemistry by L. Pataki Pb.w., C50. Ansociate Professor and E. Zapp Ph.D. 6.8e. Associate Professor Institute of Inorganic and Analytical Chemistry Eétvia Lorind University Budapest Translated by Gy. Jalsovazky © PERGAMON PRESS OXPORD SNEW VORK + TORONTO s SYDNEY + PARIS ¢ FRANKFURT Rinindai dennan ©U.K. mon Press Lid., Headington Hill Hall, Oxkind OX OBW, England on U.S.A, Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, New York 10523, U.S. A. CANADA Per of Canada Suite 104, 160 Consumers Road, will . Ontario M25 1P9, Canada AUSTRALIA — Pergamon Press (Aust,) Pty, Ltd., P.O, Box 544, Potts Point, N.S.W. 2011, Australia FRANCE Per n Pross SARL, 24 rue des Ecoles, - Paris, Codex 05, France FEDERAL Pergamon Press GmbH, 6242 Kronberg/Taunus, REPUBLIC OF Hammerwog 6, Federal Republic of Germany GERMANY Copyright © 1980 Akacémiai Kiadé Budapest All Rights Reserved. Ne thia publication be reproduced, stored sarrioolt sytem or onset in ond foros ony ang moma! decree, dearest, magnetic ape, mechanical, png, recording or otherwise, without First edition 1980 British Library Cataloguing in Publication Data Pataki, L. Basio analytical chomistey. ~ 1 Bergnrion ‘erica in analytioal chemistry 1, 2). 3° Chemistry, Analytic 1. Title TI. Zapp, E. QD75.2 543, ISBN 0-08-023850-5 Published aa a co-edition of Pergamon Prews Ltd, Oxford and Akadémiai Kinds, Budapest Printed in HungaryQUALITATIVE CHEMICAL awALrans 89 2.2.1 |Aeid groups Hydrochloric acid group Certain metal ions give precipitates with dilute hydrochloric acid or other source of ‘ide ions: Mt + Cl- = MCl(s). Excess of chloride ions forms soluble chloro complexes, w! hich came Degree risa [tly ne eomepiobely soieimectre teers) 18]: Rte MC\(s) + 2Cl~ = MCRD. ‘Tho solubility products and stability constants of some chloride MIC 20% 10-5 Ag*: AgCl is a white precipitate which, when to sunlight, i @ consequence of the formation of ete). : , very similar in behaviour to AgCl plexes or precipitate; in aqueous solutions, coppert{) ions disproportionate to copper(I) ions and copper. Rinopiapeaanaemnn eters aes ioc ee ‘tem| dependent: it is 6-7 g/dm’, 100°C it is "t vee in alkali metal hydroride solutions with ie the Rematicn of the very stable tetrahydroxoplumbete(ID) on, 5VOGEL'S TEXTBOOK OF |MACRO AND SEMIMICRO QUALITATIVE INORGANIC ANALYSIS | Fifth Edition Revised by G. Svehla, Ph.D., D.Se., F.R.LC. Reader in Analytical Chemistry, Queen's University, Belfast Longman London and New York Dipindai dengan CamScannerLongman Group Limited London Associated companies, branches and representatives throughout the world Published in the United States of America by Longman Ine., New York © Longman Group Limited 1979 All rights reserved, No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, Photocopying, recording, or otherwise, without the prior permission of the Copyright owner. First Published under the title ‘A Text-book of Qualitative Chemical Analysis’ 1937 Second Edition 1941 Reissue with Appendix 1943 Third Edition under the title ‘A Text-book of Qualitative Chemical Analysis including Semimicro Qualitative Analysis’ 1945 Fourth Edition under the title ‘A Text-book of Macro and Semimicro Qualitative Inorganic Analysis’ 1954 New Impression (with minor corrections) 1935 New Ii ‘ssion 1976 1979 Lil of Ce Cataloging in Publication Data ibrary apes Vogel's Macro and semimicro qualitative inorganic analysis. First-3d ed. published under title: A text-book of qualitative chemical analysis; 4th ed. published under title: A text-book of macro and semimicro qualitative inorganic analysis. Includes index. 1, Chemistry, Analytic-Qualitative. 2. Chemistry, Inorganic. I. Svehla, G. II. Title. III, Title: Macro and semimicro qualitative inorganic analysis. QD81.V6 1978 544 = 77-8290 ISBN 0-S82-44367-9 Printed in Great Britain by Richard Clay (The Chaucer Press) Ltd, Bungay, SuffolkCHAPTER IV REACTIONS OF THE ANIONS IV.1 SCHEME OF CLASSIFICATION The methods available for the It must, however, be mentioned that it is possible to Separate the anions into major groups dependent upon the solubilities of their silver salts, of their calcium or barium salts, and of their zinc salts; these how- ever, can only be regarded as useful in giving an indication of the limitations of the method and for the confirmation of the results obtained by the simpler procedures to be described below. __ The following scheme of classification has been found to work well in practice; one tince tome of the anions belong to more saa ce ott ions, and, furthermore, it has no theoretical basis. Essentially the processes employed may be divided into (A) those involving the identification by volatile ormcag ele pepe mint tteg hardener peal in solution. Class (A) is subdivided into (i) gases evolved acid or dilute sulphuric acid, and (ii) gases CLASS A (i) Gases evolved with dilute hydrochloric acid or dilute sulphuric acid: Carbonate, hydrogen carbonate, sulphite, thiosulphate, sulphide, nitrite, hypochlorite, cyanide, and cyanate. (ii) Gases or acid vapours evolved with concentrated sulphuric acid. These include those of (i) with the addition of the following: fluoride, hexafluorosilicate,* chloride, bromide, iodide, nitrate, chlorate (DANGER), perchlorate, permanganate (DANGER), bromate, borate," hexacyanoferrate(II), hexacyanoferrate(III), thiocyanate, formate, acetate, oxalate, tartrate, and citrate. * This is often included im Class B(i). 297 Dipindai dengan CamScannerBUKU AJAR; sassy Hak Cipta © pada penulis dan S@ UNNES BASS dilindungi Undang-Undang Penerbitan. Hak Penerbitan pada UNNES PRESS. Dicetak oleh UNNES Press. 1. Kelud Raya No. 2 Semarang 50237 Telp./Tax. (024) 8415032. iia C Kondisi lisensi dapat dilihat pada bitps:/creativecommons.orid BUKU AJAR KIMIA ANALITIK DASAR M.Alauhdin vii + 190 hal. 23,5 em. Cetakan Pertama, 2020 e-ISBN 978-602-285-244-5 ISBN 978-602-285-245-2 Sanksi PelanggaranPasal 72 Undang-andang Nomor 19 Tahun 2002 “Tentang Hak Cpa 1 pas 2ayat (1) ta psa 49 ayat (1) dan ayat (2) dipidana dengan pidanapnjara ‘masing-masing pling singhat | (at) bulan data dends paling sedikt Rp. 100 00,00 (sta ua rupah) ata pidana penara pling lara 7 (jah) tahun dant enda pling banyak Rp. '5.00.000.000,0 (ina Miya) Baangspa dengan songaja menyatkan, memamerkan, mengedaskan atau menjual. kepada ‘uum sua ciptan atau barang asl planggaran Hak Cipt schagaimanadimaksud dalam at (1) ipdana dengan pidana penjara paling lara 5 (lima) tah dan atau dena paling banyak Rp 50.00,000.00 (imap jt up),ABV ANALISIS KATION DAN ANION Bab ini akan membahas analisis kualitatif untuk menentukan keberadaan kkation dan anion dalam suatu bahan (larutan). Pembahasan diawali dengan penggolongan kation dan pemisahan kation-kation ke dalam golongannya. Pembshasan dilanjutkan dengan analisis anion disertai dengan contoh- contohny: ‘Sub-Capaian Pembelajaran Mata Kuliah Setelah mempelajari bab ini, mahasiswa diharapkan dapat: 1, Mengidentifikasi dan mengklasifikasikan kation-kation berdasarkan golongannya 2. Memprediksi keberadaan Kation-kation secara kualitatif dalam suatu Iarutan 3. Merancang suatu prosedur untuk mengidentifikasi suatu kation golongan 1 dan 2 4, Mengidentfikasi jenis-jenis anion untuk keperluan analisis kualitatif| 1. PENDAHULUAN ‘Analisis kualitatif kation dan anion dilakukan dengan mengamati kkarakteristik reaksi kimia yang terjadi pada sampel bahan yang dianalisis. Analisis dapat dilakukan dengan metode reaksi kering (dry reactions) atau ‘metode reaksi basah (wer reactions). Reaksi kering biasanya diterapkan pada sampel padat sedangkan reaksi basah untuk sampel yang berupa lata, Scbelum menentukan prosedur analisis, pemeriksaan pendahuluan dapat dilakukan, misalnya dengan mengamati secara langsung warna atau bau dari zat yang dianalisis. Warna larutan dapat digunakan sebagai identifikasi awal Keberadaan suatu ion (biasanya ation terhidrat). 50Keberadaan ion tembaga(Il) biasanya memberikan warna biru pada larutannya, sedangkan warna hijau dapat muncul pada larutan kromium(II1). Wama kuning dapat menunjukkan adanya kromat, heksasianoferat(II), atau besi(I), sedangkan larutan berwama ungu dapat ddiduga mengandung permanganat. Uji nyala Salah satu metode reaksi kering dalam analisis kualitatif adalah uji nyala (fame test). Logam atau ion logam yang dipanaskan pada temperatur tinggi akan berada pada keadaan tereksitasi karena elektron berpindah ke tingkat energi yang lebih tinggi. Keadaan ini tidak stabil, sehingga elektron cenderung kembali ke keadaan dasar dengan mengemisikan energi yang berupa sinar tampak. Setiap unsur memiliki spektrum emisi sinar tampak yang khas sehingga akan memunculkan wama yang berbeda untuk setiap lunsur. Dengan demikian, keberadaan suatu unsur dapat diketahui berdasarkan warna-warna yang teramati. Namun, pengamatan dengan ‘mata telanjang sangat terbatas, sehingga tidak banyak unsur yang dapat diamati dengan cara ini, Proses emisi seperti inilah yang kemudian dijadikan salah satu dasar untuk analisis secara spektrofotometri, Namun, topik ini di luar cakupan buku in. Uji nyala dilakukan menggunakan kawat patina atau kawat nikel- kromium (nikrom). Kawat platina harus dipijarkan terlebih dahulu sampai tidak mewamai api sebelum digunakan dan dicuci dengan HCI pekat Selanjutnya, kawat platina dicelupkan ke dalam larutan ataupun padatan (serbuk) bahan yang akan dianalisis dan dipanaskan di bagian luar api dari pembakar Bunsen. Uap yang dilepaskan dari pemanasan itu akan ‘menyebabkan api berwama yang waranya akan tergantung pada jenis kation yang ada (Tabel 5.1). 31‘Amin and Lim, ALCHEMY Jumal Peacitan Kimia, Vol1S(1) 2019, 138-149, jiciizwy arse ‘Laman resmi: ps:/jumal.unsac idalchemy Ton Chromatographic Method for the Simultaneous Determination of Anions and Cations in Firecrackers and Matches Samples as Known Potential Explosives Muhammad Amin* and Lee Wah Lim? * Study Program of Chemistry Education, Faculty of Teacher Training and Education, Universitas Khairun, Jalan Bandara Babullah, Akehuda, Ternate 97723, North Maluku, Indonesia "Department of Chemistry and Biomolecular Science, Faculty of Engineering. Gifu University, I-1 Yanagido, Gifu 501-1193, Japan * Corresponding author Exmail: nwh_amin @unkhair-acid OM: 10.2096 Valchemy.15.1.27570.138-149 Received 02 February 2019, Accepied 27 February 2019, Published 01 March 2019 ABSTRACT A reference ion chromatography method based on column switching has been presented for the simultaneous determining anions (CI, CIO; , NOs, SO," and NOs ) and/or cations (NH,’, Na’, K’, C and Mg") using one pump, one type of mobile phase, and one detector. The reference method performed anion-exchange column and cation-exchange column and arranged serially via one 10-port valve. The determination of either anions or cations in one determination system could be made by switching the valve. ‘When the use of 1.25 mM trimellitic acid as a mobile phase and the instrument was operated at a flow rate of 0.6 mL/min, five anions and five cations were determined on the anion-exchange column and the cation- exchange column, respectively. All anions target could be determined completely within 55 minutes, whereas the cations target could be determined within 35 minutes. The calculation of limit of detection using $/N= ‘was 3.85 ~ 14.10 4M for anions and 2.95 ~ 10.58 JM for cations. The relative standard deviations of all ions were less than 3.82%, 3.29%, and 3.21% for retention time, peak area, and peak height, respectively. The reference method was then applied for the simultaneous determining anions and/or cations contained in firecrackers and matches samples as known potentially explosives. Keywords: anions and cations, column switching, firecrackers, ion chromatography, matches INTRODUCTION Since ion chromatography (IC) method was first introduced by Small er al. in 1975, (Weiss, 1995), now become an excellent analytical tool for determining inorganic ions in forensic sciences (Doyle and McCord, 1998; Hopper et al., 2005; Feng et al., 2008; Johns et al., 2008; Meng et al, 2008), counter-terrorism (Amin, 2014; Mishra and Jaiswal, 2017), and the most application is in the environmental water monitoring (Ohta, ef al., 1996; Jackson et al., 2003). A conventional, anions and cations are determined separately 138 (Copyright ©2019, ALCHEMY Jural Pelian Kimi, ISSN 1412-4002, ¢ ISSN 2443-4183,‘Amin and Lim, ALCHEMY Jal Penelian Kins, Vol 1(1) 2009, 138-149, using different determination optimum conditions. And a number of published papers have been discussed for determining simultaneously both anions and cations in a one determination system due to a potential to increase the efficiency of ion chromatographic determination in a laboratory work (Jones and Tarter, 1984; Saari-Nordhaus and Anderson, 1991; Amin, et al., 2007; 2008). Fast identification of inorganic ions in explosives materials is an important factor for counterterrorism procedures. The main analytical techniques have been used for the determination of ionic components related to explosive samples such as. capillary electrophoresis (CE) (Doyle and Mccord, 1998), capillary zone electrophoresis (CZE) (Hopper et al., 2005; Feng ef al., 2008), and IC (Johns et al., 2008). CE promises faster separation and low cost of operation. However, it offered poorer detection sensitivity in their analysis. IC is currently used in many wide ranges of application including the detection of cations and anions presented in explosives and potentially explosives samples. such as firecrackers and fireworks (Amin, 2014). Referring to the recent development, there are at least two approaches known for determining simultaneously anions and cations in one arrangement determination system, namely (1) using one column which allows partially determining simultaneously anions and ¢: ‘ions (Iskandarani and Miller, 1985; Jones and Tarter, 1984; Saari-Nordhaus and Anderson, 1991), and (2) using two analytical separators parallelly- and seriesly-connected with or without column switching (Amin, ef al, 2007; 2008). For the latter, in which there is no column switching, an appropriate mobile phase should be considered for the simultaneous determining both cations and anions. However, the obtained anions and cations peaks often overlapped; therefore, it is not a promising method anymore. In 2008, Meng et al. suggested an alternative method for the simultaneously determining cations and anions normally found in explosive residues samples which can be achieved by connecting directly cation-exchange/anion-exchange analytical columns with the series arrangement. However, it gave the poor selectivity of anions and not satisfactory baseline separation for anion peaks under the chosen mobile phase (Meng et al., 2008). The most advantage of the column switching method is the ability for simultaneous determining cations and anions in one determination arrangement system in terms of providing better peaks shape and selectivity without peaks overlapping. An IC method based on column switching is intended to use two columns arranged in series in a single determination system. In this case, the cation-exchange column was prepared to determine the cations concentration in the samples, while the anion-exchange column was prepared to 139 Copyright ©2019, ALCHEMY Jural Peelian Kimi, ISSN 1412-4002, ¢ ISSN 2443-4183,VOGEL'S