SMALL-SCALE SYNTHESIS of LABORATORY REAGENTS with Reaction Modeling © 2011 by Taylor and Francis Group, LLC SMALL-SCALE SYNTHESIS of LABORATORY REAGENTS with Reaction Modeling LEONID LERNER Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business © 2011 by Taylor and Francis Group, LLC CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2011 by Taylor and Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number: 978-1-4398-1312-6 (Hardback) This book contains information obtained from authentic and highly regarded sources. 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For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright. com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Lerner, Leonid. Small-scale synthesis of laboratory reagents with reaction modeling / Leonid Lerner. p. cm. Summary: “The in-lab preparation of some chemical reagents provides a number of advantages over purchasing commercially-prepared samples. This volume contains a detailed description of methods for the rapid and reliable synthesis of many useful reagants that are otherwise difficult to obtain. It provides spectroscopic analyses of products, presents the thermodynamic/kinetic data of reactions, and offers a thorough analysis of the purity of the final products. Enhanced by useful diagrams and photographs, this text is a valuable reference for researchers in small or remote laboratories”-- Provided by publisher. Summary: “When working in a small chemical laboratory attached to a non-chemistry specific project one is frequently asked to solve problems which occur in the main project. Usually one can think of several solutions and experimental testing is required to choose between the different approaches, or indeed to find an approach that works. These often require the use of small amounts of chemicals which the laboratory does not stock. Obtaining these chemicals from commercial suppliers in a suitable timeframe sometimes poses problems. This is particularly the case in isolated regions such as Australasia, when the supplier has no local stocks of hazardous substances and they have to be brought in from overseas, something which can introduce delays from several weeks to six months or more. Since there is no certainty that the substance whose acquisition is introducing the delay will form part of the ultimate solution, this delay is particularly objectionable. The primary aim of this book is therefore to provide reliable laboratory syntheses of the most common reagents whose acquisition can introduce delays due to their hazardous nature. It is apparent that there is little point in replacing delays in reagent purchase with uncertainties in their synthesis, hence the preparations presented in this book were chosen with the following criteria in mind: short duration, availability of apparatus, high yield, and high purity of the product. It was also considered necessary for the syntheses to be described in greater detail than is normally provided in the literature, since I have frequently found that omission of apparently small details can subsequently waste much time”-- Provided by publisher. Includes bibliographical references and index. ISBN 978-1-4398-1312-6 (hardback) 1. Chemical tests and reagents--Synthesis. I. Title. QD77.L47 2011 543.028’4--dc22 2010038460 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com © 2011 by Taylor and Francis Group, LLC Contents Preface.......................................................................................................................xi About the Author .....................................................................................................xv 1Chapter 1Chapter Safety in the Laboratory .......................................................................1 1.1 Introduction ...............................................................................1 1.2 Characteristics of Hazardous Substances Prepared in This Book ..............................................................................2 1.2.1 Sodium .........................................................................2 1.2.2 Potassium......................................................................4 1.2.3 Lithium .........................................................................5 1.2.4 Cesium ..........................................................................6 1.2.5 Lithium and Sodium Hydrides .....................................6 1.2.6 Aluminum Bromide .....................................................6 1.2.7 Lithium Aluminum Hydride ........................................7 1.2.8 Diethylaluminum Bromide and Triethylaluminum .........................................................7 1.2.9 Hydrazine Hydrate .......................................................7 1.2.10 Azides ...........................................................................8 1.2.11 n-Butyllithium 2M in Hexane ......................................8 1.2.12 Potassium Hydride .......................................................8 1.2.13 Carbon Disulfide ..........................................................8 1.2.14 Hydrogen Sulfide ..........................................................9 1.2.15 Carbon Tetrachloride and Chloroform .........................9 1.2.16 Triphosgene ..................................................................9 1.2.17 Phosphorus Trichloride, Oxychloride, and Pentachloride .............................................................. 10 1.2.18 Sulfur Trioxide and Oleum ........................................ 10 1.2.19 Thionyl Chloride ........................................................ 11 1.2.20 Sulfur Chlorides ......................................................... 11 1.2.21 Chlorosulfonic Acid and Pyrosulfuryl Chloride ........12 Reference ............................................................................................12 2Chapter 2Chapter Sodium ............................................................................................... 13 Summary ............................................................................................ 13 Applications ....................................................................................... 13 2.1 Introduction ............................................................................. 13 2.2 Discussion ................................................................................ 14 2.2.1 Basics of Cell Operation ............................................. 14 2.2.2 Cell Regimes ..............................................................15 v © 2011 by Taylor and Francis Group, LLC vi Contents 2.2.3 Cell Equation .............................................................. 18 2.2.3.1 Preliminaries .............................................. 18 2.2.3.2 Relation between Drop Volume and Surface Area ............................................... 19 2.2.3.3 Deriving the Cell Equation .........................20 2.2.4 Thermal Balance ........................................................24 2.2.5 Time Required for Melting ........................................25 2.2.6 Cell Corrosion ............................................................26 2.3 Experimental ...........................................................................26 2.3.1 Introduction ................................................................26 2.3.2 Setup and Operation ...................................................27 References ..........................................................................................30 3Chapter 3Chapter Potassium............................................................................................ 33 Summary ............................................................................................ 33 Applications