DIAZOTIZATION OF ALIPHATIC AND AROMATIC AMINES by Lorraine Zolton A Dissertation ...

128 Pages·2012·3.81 MB·English

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.
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Download date 09/10/2018 11:10:41
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
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Dissertation Director Date
After inspection of the dissertation, the following members
of the Final Examination Committee concur in its approval and
recommend its acceptance:*
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*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
pK Determinations . 37
a
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