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DIAZOTIZATION of ALIPHATIC and AROMATIC AMINES by Lorraine Zolton a Dissertation Submitted to the Faculty of the DEPARTMENT of C DIAZOTIZATION OF ALIPHATIC AND AROMATIC AMINES Item Type text; Dissertation-Reproduction (electronic) Authors Zolton, Lorraine, 1935- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 06/10/2021 13:37:07 Link to Item http://hdl.handle.net/10150/284456 DIAZOTIZATION OF ALIPHATIC AND AROMATIC AMINES by Lorraine Zolton A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College UNIVERSITY OF ARIZONA 1962 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by Lorraine Zolf.on entitled Tin n^oti znti on of' A 1 i p'nat.i r nnrl -y om-t-.i r Aminos be accepted as fulfilling the dissertation requirement of the degree of Doctor of Philosophy •• "> . - . _ - <- ••• --tr.K. j... i, • ,• y Dissertation Director Date After inspection of the dissertation, the following members of the Final Examination Committee concur in its approval and recommend its acceptance:* i : — . .. 1 /(jM//1 2<J. /, // . : ? ;• v-''' - • <• - /j. .• G/i£ / >7 (lei, J 1YU • j I 1 (. (• ^ i 1 t - •;••• •> *This approval and acceptance is contingent on the candidate's adequate performance and defense of this dissertation at the final oral examination. The inclusion of this sheet bound into the library copy of the dissertation is evidence of satisfactory performance at the final examination. STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in The University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be'granted by the head of the major department or the Dean of the Graduate College when in their judgment the proposed use of the material is in the inter­ ests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: ii ACKNOWLEDGMENT The author wishes to express her appreciation to Dr. Alec E. Kelley for his advice and patience during the course of this research. iii TABLE OF CONTENTS Page LIST OF TABLES vi LIST OF FIGURES x ABSTRACT xii INTRODUC TION 1 The Order of the Reaction and the Nitrosating Species 1 Nitrous Acid Decomposition 8 The Effect of the Acid Concentration 9 The Effect of Buffers and Added Anions 11 The Reaction in Strongly Acidic Solutions 14 A Carbonium Ion as an Intermediate 16 Causes of Conflict in the ^Literature 20 STATEMENT OF PROBLEM 25 EXPERIMENTAL 27 Materials . 27 Solutions 30 Apparatus 31 Procedure 33 Aromatic Amines . 33 Aliphatic Amines 35 pKa Determinations . 37 Calculations . 38 Correction of Gas Volume 38 Correction for Nitrous Acid Decomposition...., 39 Determination of Reaction Order 40 Rate Constants... 41 Ionic Strength 44 iv TABLE OF CONTENTS (Continued) Page Hydrogen Ion Concentration Determination in the Presence of Fluoride Ions 44 Theoretical Curves for Possible Reacting Species in the Diazotization of Aniline 45 DISCUSSION AND RESULTS 50 Fluoride Buffer 50 Order in Aniline and Nitrous Acid 51 Order in Ammonia and Nitrous Acid 60 Stoichiometric and Molecular Rate Constants for the Reaction of Aniline with Nitrous Acid 74 Theoretical Curves for Possible Reacting Species 79 Effect of Ionic Strength for Reaction of Aniline with Nitrous Acid 82 Activation Energies for the Reaction of Aniline with Nitrous Acid 82 Rate Constants for the Reaction of Ammonia with Nitrous Acid 86 Effect of Ionic Strength for Reaction of Ammonia with Nitrous Acid • 86 Activation Energy for Reaction of Ammonia with Nitrous Acid 90 pK^ Values for Some Amines 90 Reaction of Aliphatic Amines with Nitrous Acid 93 Comparison of the Molecular Rate Constants for the Reaction of Amines with Nitrous Acid 98 SUMMARY 105 BIBLIOGRAPHY Ill v LIST OF TABLES Table age 1 Effect of Fluoride Buffer Concentration on the Reaction of Ammonia with Nitrous Acid 52 2 Effect of Fluoride Buffer Concentration on the Reaction of Aniline with Nitrous Acid 52 3 Effect of Nitrous Acid Concentration on Reaction with Aniline at pH 1.5 53 4 Effect of Aniline Concentration on Reaction with Nitrous Acid at pH 1.5 53 5 Effect of Nitrous Acid Concentration on Reaction with Aniline at pH 2 54 6 Effect of Aniline Concentration on Reaction with Nitrous Acid at pH 2 54 7 Effect of Nitrous Acid Concentration on Reaction with Aniline at pH 3 55 8 Effect of Aniline Concentration on Reaction with Nitrous Acid at pH 3 55 9 Effect of Nitrous Acid Concentration on Reaction with Aniline at pH 4 56 10 Effect of Aniline Concentration on Reaction with Nitrous Acid at pH 4 56 11 Effect of Nitrous Acid Concentration on Reaction with Ammonia at pH 4 61 12 Effect of Ammonia Concentration on Reaction with Nitrous Acid at pH 4 61 vi LIST OF TABLES (Continued) Table Page 13 Effect of Ammonia Concentration on Reaction with Nitrous Acid at pH 3 62 14 Effect of Nitrous Acid Concentration on Reaction with Ammonia at pH 3 62 15 Effect of Nitrous Acid Concentration on Reaction with Ammonia at pH 2 63 16 Lack of Participation of Ammonia in Reaction at pH 1 and 2 63 17 Amount of Evolved Gas Representing Nitrous Acid Decomposition 67 18 Phosphate Buffer Catalysis in Reaction of Nitrous Acid with Ammonia 69 19 Effect of Ammonia Concentration on Reaction with Nitrous Acid in the Presence of Phosphate Buffer 70 20 Effect of Nitrous Acid Concentration on Reaction with Ammonia in the Presence of Phosphate Buffer 70 21 Stoichiometric and Molecular Third Order Rate Constants for Reaction of Aniline with Nitrous Acid at pH 1.5 75 22 Stoichiometric and Molecular Third Order Rate Constants for Reaction of Aniline with Nitrous Acid at pH 2 75 23 Stoichiometric and Molecular Second Order Rate Constants for Reaction of Aniline with Nitrous Acid at pH 3 76 24 Stoichiometric and Molecular Second Order Rate Constants for Reaction of Aniline with Nitrous Acid at pH 4 76 vii LIST OF TABLES (Continued) Table Page 25 Absence of Acid Catalysis in Reaction of Aniline with Nitrous Acid 78 26 Determination of Reacting Species at Several pH Values from Theoretical Curves in Reaction of Aniline with Nitrous Acid 80 27 Effect of Ionic Strength on Reaction of Aniline with Nitrous Acid 83 28 Activation Energies for Reaction of Nitrous Acid with Aniline 85 29 Third Order Rate Constants for Reaction of Ammonia with Nitrous Acid at pH 4 87 30 Third Order Rate Constants for Reaction of Ammonia with Nitrous Acid at pH 3 88 31 Effect of Ionic Strength on Reaction of Ammonia with Nitrous Acid at pH 4 89 32 Activation Energy for Reaction of Ammonia with Nitrous Acid at pH 4 89 33 pK Values for the Conjugate Acids of Some Ammo Compounds 92 34 Variation of Rate Constant with Temperature for Reaction of n-Butylamine with Nitrous Acid 94 35 Variation of Rate Constant with Temperature for Reaction of Isobutylamine with Nitrous Acid 94 36 Variation of Rate Constant with Temperature for Reaction of sec-Butylamine with Nitrous Acid 95 37 Variation of Rate Constant with Temperature for Reaction of t-Butylamine with Nitrous Acid 95 viii LIST OF TABLES (Continued) Table Page 38 Variation of Rate Constant with Temperature for Reaction of Neopentylamine with Nitrous Acid 96 39 Activation Energies and Rate Constants at 20° for Reactions of Amines with Nitrous Acid 97 40 Enthalpy, Free Energy, and Entropy of Activation.... 103 » ix LIST OF FIGURES Figure Page 1 Apparatus for studies of the diazotization of aliphatic amines 32 2 Order in aniline at pH 1.5 57 3 Order in nitrous acid at pH 1.5 57 4 Order in aniline at pH 2 58 5 Order in nitrous acid at pH 2 58 6 Order in nitrous acid at pH 3 59 7 Order in nitrous acid at pH 4 59 8 Order in ammonia for reaction with nitrous acid at pH 4 64 9 Order in nitrous acid for reaction with ammonia at pH 4 64 10 Order in ammonia for reaction with nitrous acid at pH 3 65 11 Order in nitrous acid for reaction with ammonia at pH 3 65 12 Order in nitrous acid for reaction with ammonia in presence of phosphate buffer at pH 3 71 13 Phosphate buffer dependence for reaction of ammonia with nitrous acid at pH 3 71 2E LIST OF FIGURES (Continued) Figure Page 14 Theoretical curves for amine and nitrosonium ion as reaction species and decomposition of nitrous acid 73 15 Theoretical curves for reaction of aniline with nitrous acid 81 16 Activation energies for reaction of aniline with nitrous acid at pH 1.5, 2, 3, and 4.„ 84 17 Activation energies for reaction of ammonia with nitrous acid at pH 4 91 18 Activation energies for reaction of n-butyl, sec- butyl, and t-butylamines with nitrous acid at pH 4..... 99 19 Activation energies for reaction of isobutyl and neopentylamines with nitrous acid at pH 4 100 xi ABSTRACT DIAZOTIZATION OF ALIPHATIC AND AROMATIC AMINES by Lorraine Zolton The mechanism of diazotization of aliphatic and aromatic amines was studied in order to resolve some of the controversy existing in the literature.
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