|
|
Physical-Chemical Properties and Environmental Fate for Organic Chemicals
Second Edition
HANDBOOK OF © 2006 by Taylor & Francis Group, LLC
Volume I Introduction and Hydrocarbons
Volume II Halogenated Hydrocarbons
Volume III Oxygen Containing Compounds
Volume IV Nitrogen and Sulfur Containing Compounds and Pesticides
A CRC title, part of the Taylor & Francis imprint, a member of the
Taylor & Francis Group, the academic division of T&F Informa plc.
Boca Raton London New York
Physical-Chemical
Properties and
Environmental Fate for
Organic Chemicals
Volume I
Introduction and Hydrocarbons
Donald Mackay
Wan Ying Shiu
Kuo-Ching Ma
Sum Chi Lee
Second Edition
HANDBOOK OF
Volume II
Halogenated Hydrocarbons
Volume III
Oxygen Containing Compounds
Volume IV
Nitrogen and Sulfur Containing Compounds
and Pesticides
© 2006 by Taylor & Francis Group, LLC
Published in 2006 by
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2006 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group
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-10: 1-56670-687-4 (Hardcover)
International Standard Book Number-13: 978-1-56670-687-2 (Hardcover)
Library of Congress Card Number 2005051402
This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are
indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the
publisher cannot assume responsibility for the validity of all materials or for the consequences of their use.
No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known
or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission
from the publishers.
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
Handbook of physical-chemical properties and environmental fate for organic chemicals.--2nd ed. / by Donald Mackay ... [et al.].
p. cm.
Rev. ed. of: Illustrated handbook of physical-chemical properties and environmental fate for organic chemicals / Donald Mackay,
Wan Ying Shiu, and Kuo Ching Ma. c1992-c1997.
Includes bibliographical references and index.
ISBN 1-56670-687-4 (set : acid-free paper)
1. Organic compounds--Environmental aspects--Handbooks, manuals, etc. 2. Environmental chemistry--Handbooks, manuals, etc.
I. Mackay, Donald, 1936- II. Mackay, Donald, 1936- Illustrated handbook of physical-chemical properties and environmental fate
for organic chemicals.
TD196.O73M32 2005
628.5'2--dc22 2005051402
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com Taylor & Francis Group is the Academic Division of T&F Informa plc.
© 2006 by Taylor & Francis Group, LLC
Preface
This handbook is a compilation of environmentally relevant physical-chemical data for similarly structured groups of
chemical substances. These data control the fate of chemicals as they are transported and transformed in the multimedia
environment of air, water, soils, sediments, and their resident biota. These fate processes determine the exposure experienced
by humans and other organisms and ultimately the risk of adverse effects. The task of assessing chemical fate locally,
regionally, and globally is complicated by the large (and increasing) number of chemicals of potential concern; by
uncertainties in their physical-chemical properties; and by lack of knowledge of prevailing environmental conditions
such as temperature, pH, and deposition rates of solid matter from the atmosphere to water, or from water to bottom
sediments. Further, reported values of properties such as solubility are often in conflict. Some are measured accurately,
some approximately, and some are estimated by various correlation schemes from molecular structures. In some cases,
units or chemical identity are wrongly reported. The user of such data thus has the difficult task of selecting the “best”
or “right” values. There is justifiable concern that the resulting deductions of environmental fate may be in substantial
error. For example, the potential for evaporation may be greatly underestimated if an erroneously low vapor pressure
is selected.
To assist the environmental scientist and engineer in such assessments, this handbook contains compilations of
physical-chemical property data for over 1000 chemicals. It has long been recognized that within homologous series,
properties vary systematically with molecular size, thus providing guidance about the properties of one substance from
those of its homologs. Where practical, plots of these systematic property variations can be used to check the reported
data and provide an opportunity for interpolation and even modest extrapolation to estimate unmeasured properties of
other substances. Most handbooks treat chemicals only on an individual basis and do not contain this feature of chemicalto-
chemical comparison, which can be valuable for identifying errors and estimating properties. This most recent edition
includes about 1250 compounds and contains about 30 percent additional physical-chemical property data. There is a
more complete coverage of PCBs, PCDDs, PCDFs, and other halogenated hydrocarbons, especially brominated and
fluorinated substances that are of more recent environmental concern. Values of the physical-chemical properties are
generally reported in the literature at a standard temperature of 20 or 25°C. However, environmental temperatures vary
considerably, and thus reliable data are required on the temperature dependence of these properties for fate calculations.
A valuable enhancement to this edition is the inclusion of extensive measured temperature-dependent data for the first
time. The data focus on water solubility, vapor pressure, and Henry’s law constant but include octanol/water and octanol/air
partition coefficients where available. They are provided in the form of data tables and correlation equations as well as
graphs.
We also demonstrate in Chapter 1 how the data may be taken a stage further and used to estimate likely environmental
partitioning tendencies, i.e., how the chemical is likely to become distributed between the various media that comprise
our biosphere. The results are presented numerically and pictorially to provide a visual impression of likely environmental
behavior. This will be of interest to those assessing environmental fate by confirming the general fate characteristics or
behavior profile. It is, of course, only possible here to assess fate in a “typical” or “generic” or “evaluative” environment.
No claim is made that a chemical will behave in this manner in all situations, but this assessment should reveal the
broad characteristics of behavior. These evaluative fate assessments are generated using simple fugacity models that
flow naturally from the compilations of data on physical-chemical properties of relevant chemicals. Illustrations of
estimated environmental fate are given in Chapter 1 using Levels I, II, and III mass balance models. These and other
models are available for downloading gratis from the website of the Canadian Environmental Modelling Centre at Trent
University (www.trent.ca/cemc).
It is hoped that this new edition of the handbook will be of value to environmental scientists and engineers and to
students and teachers of environmental science. Its aim is to contribute to better assessments of chemical fate in our
multimedia environment by serving as a reference source for environmentally relevant physical-chemical property data
of classes of chemicals and by illustrating the likely behavior of these chemicals as they migrate throughout our biosphere.
© 2006 by Taylor & Francis Group, LLC
Acknowledgments
We would never have completed the volumes for the first and second editions of the handbook and the CD-ROMs
without the enormous amount of help and support that we received from our colleagues, publishers, editors, friends,
and family. We are long overdue in expressing our appreciation.
We would like first to extend deepest thanks to these individuals: Dr. Warren Stiver, Rebecca Lun, Deborah Tam,
Dr. Alice Bobra, Dr. Frank Wania, Ying D. Lei, Dr. Hayley Hung, Dr. Antonio Di Guardo, Qiang Kang, Kitty Ma,
Edmund Wong, Jenny Ma, and Dr. Tom Harner. During their past and present affiliations with the Department of
Chemical Engineering and Applied Chemistry and/or the Institute of Environment Studies at the University of Toronto,
they have provided us with many insightful ideas, constructive reviews, relevant property data, computer know-how,
and encouragement, which have resulted in substantial improvements to each consecutive volume and edition through
the last fifteen years.
Much credit goes to the team of professionals at CRC Press/Taylor & Francis Group who worked on this second
edition. Especially important were Dr. Fiona Macdonald, Publisher, Chemistry; Dr. Janice Shackleton, Input Supervisor;
Patrica Roberson, Project Coordinator; Elise Oranges and Jay Margolis, Project Editors; and Marcela Peres, Production
Assistant.
We are indebted to Brian Lewis, Vivian Collier, Kathy Feinstein, Dr. David Packer, and Randi Cohen for their
interest and help in taking our idea of the handbook to fruition.
We also would like to thank Professor Doug Reeve, Chair of the Department of Chemical Engineering and Applied
Chemistry at the University of Toronto, as well as the administrative staff for providing the resources and assistance
for our efforts.
We are grateful to the University of Toronto and Trent University for providing facilities, to the Natural Sciences
and Engineering Research Council of Canada and the consortium of chemical companies that support the Canadian
Environmental Modelling Centre for funding of the second edition. It is a pleasure to acknowledge the invaluable
contributions of Eva Webster and Ness Mackay.
© 2006 by Taylor & Francis Group, LLC
Biographies
Donald Mackay, born and educated in Scotland, received his degrees in Chemical Engineering from the University of
Glasgow. After working in the petrochemical industry he joined the University of Toronto, where he taught for 28 years
in the Department of Chemical Engineering and Applied Chemistry and in the Institute for Environmental Studies. In
1995 he moved to Trent University to found the Canadian Environmental Modelling Centre. Professor Mackay’s primary
research is the study of organic environmental contaminants, their properties, sources, fates, effects, and control, and
particularly understanding and modeling their behavior with the aid of the fugacity concept. His work has focused
especially on the Great Lakes Basin; on cold northern climates; and on modeling bioaccumulation and chemical fate
at local, regional, continental and global scales.
His awards include the SETAC Founders Award, the Honda Prize for Eco-Technology, the Order of Ontario, and
the Order of Canada. He has served on the editorial boards of several journals and is a member of SETAC, the American
Chemical Society, and the International Association of Great Lakes Research.
Wan-Ying Shiu is a Senior Research Associate in the Department of Chemical Engineering and Applied Chemistry,
and the Institute for Environmental Studies, University of Toronto. She received her Ph.D. in Physical Chemistry from
the Department of Chemistry, University of Toronto, M.Sc. in Physical Chemistry from St. Francis Xavier University,
and B.Sc. in Chemistry from Hong Kong Baptist College. Her research interest is in the area of physical-chemical
properties and thermodynamics for organic chemicals of environmental concern.
Kuo-Ching Ma obtained his Ph.D. from Florida State University, M.Sc. from The University of Saskatchewan, and
B.Sc. from The National Taiwan University, all in Physical Chemistry. After working many years in the aerospace,
battery research, fine chemicals, and metal finishing industries in Canada as a Research Scientist, Technical Supervisor/
Director, he is now dedicating his time and interests to environmental research.
Sum Chi Lee received her B.A.Sc. and M.A.Sc. in Chemical Engineering from the University of Toronto. She has
conducted environmental research at various government organizations and the University of Toronto. Her research
activities have included establishing the physical-chemical properties of organochlorines and understanding the sources,
trends, and behavior of persistent organic pollutants in the atmosphere of the Canadian Arctic.
Ms. Lee also possesses experience in technology commercialization. She was involved in the successful commercialization
of a proprietary technology that transformed recycled material into environmentally sound products for the
building material industry. She went on to pursue her MBA degree, which she earned from York University’s Schulich
School of Business. She continues her career, combining her engineering and business experiences with her interest in
the environmental field.
© 2006 by Taylor & Francis Group, LLC
Contents
Volume I
Chapter 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Chapter 2 Aliphatic and Cyclic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Chapter 3 Mononuclear Aromatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
Chapter 4 Polynuclear Aromatic Hydrocarbons (PAHs) and Related Aromatic Hydrocarbons . . . . . . . . . . . . . . 617
Volume II
Chapter 5 Halogenated Aliphatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
Chapter 6 Chlorobenzenes and Other Halogenated Mononuclear Aromatics . . . . . . . . . . . . . . . . . . . . . . . . . . . 1257
Chapter 7 Polychlorinated Biphenyls (PCBs). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1479
Chapter 8 Chlorinated Dibenzo-p-dioxins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2063
Chapter 9 Chlorinated Dibenzofurans. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2167
Volume III
Chapter 10 Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2259
Chapter 11 Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2473
Chapter 12 Aldehydes and Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2583
Chapter 13 Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2687
Chapter 14 Phenolic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2779
Chapter 15 Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3023
Volume IV
Chapter 16 Nitrogen and Sulfur Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3195
Chapter 17 Herbicides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3457
Chapter 18 Insecticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3711
Chapter 19 Fungicides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4023
Appendix 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4133
Appendix 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4137
Appendix 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4161
© 2006 by Taylor & Francis Group, LLC
16 Nitrogen and Sulfur Compounds
CONTENTS
16.1 List of Chemicals and Data Compilations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3197
16.1.1 Nitriles (Organic cyanides) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3197
16.1.1.1 Acetonitrile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3197
16.1.1.2 Propionitrile. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3203
16.1.1.3 Butyronitrile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3207
16.1.1.4 Acrylonitrile (2-Propenenitrile) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3210
16.1.1.5 Benzonitrile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3214
16.1.2 Aliphatic amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3218
16.1.2.1 Dimethylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3218
16.1.2.2 Trimethylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3222
16.1.2.3 Ethylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3225
16.1.2.4 Diethylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3228
16.1.2.5 n-Propylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3231
16.1.2.6 n-Butylamine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3234
16.1.2.7 Ethanolamine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3236
16.1.2.8 Diethanolamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3239
16.1.2.9 Triethanolamine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3241
16.1.3 Aromatic amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3243
16.1.3.1 Aniline. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3243
16.1.3.2 2-Chloroaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3249
16.1.3.3 3-Chloroaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3253
16.1.3.4 4-Chloroaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3257
16.1.3.5 3,4-Dichloroaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3261
16.1.3.6 o-Toluidine (2-Methylbenzeneamine). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3263
16.1.3.7 m-Toluidine (3-Methylbenzeneamine) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3267
16.1.3.8 p-Toluidine (4-Methylbenzeneamine). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3270
16.1.3.9 N,N.-Dimethylaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3274
16.1.3.10 2,6-Xylidine (2,6-Dimethylbenzeneamine) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3277
16.1.3.11 Diphenylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3279
16.1.3.12 Benzidine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3283
16.1.3.13 3,3.-Dichlorobenzidine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3285
16.1.3.14 N,N.-Bianiline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3287
16.1.3.15 .-Naphthylamine (1-Aminonaphthalene). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3289
16.1.3.16 .-Naphthylamine (2-Aminonaphthalene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3291
16.1.3.17 2-Nitroaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3293
16.1.3.18 4-Nitroaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3295
16.1.4 Nitroaromatic compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3297
16.1.4.1 Nitrobenzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3297
16.1.4.2 2-Nitrotoluene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3304
16.1.4.3 4-Nitrotoluene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3308
16.1.4.4 2,4-Dinitrotoluene (DNT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3313
© 2006 by Taylor & Francis Group, LLC
3196 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
16.1.4.5 2,6-Dinitrotoluene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3317
16.1.4.6 2,4,6-Trinitrotoluene (TNT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3320
16.1.4.7 1-Nitronaphthalene (.-Nitronaphthalene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3326
16.1.5 Amides and ureas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3328
16.1.5.1 Acetamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3328
16.1.5.2 Acrylamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3330
16.1.5.3 Benzamide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3331
16.1.5.4 Urea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3333
16.1.6 Nitrosamines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3336
16.1.6.1 N-Nitrosodimethylamine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3336
16.1.6.2 N-Nitrosodipropylamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3338
16.1.6.3 Diphenylnitrosoamine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3340
16.1.7 Heterocyclic compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3342
16.1.7.1 Pyrrole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3342
16.1.7.2 Indole. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3346
16.1.7.3 Pyridine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3348
16.1.7.4 2-Methylpyridine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3354
16.1.7.5 3-Methylpyridine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3358
16.1.7.6 2,3-Dimethylpyridine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3362
16.1.7.7 Quinoline. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3365
16.1.7.8 Isoquinoline. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3369
16.1.7.9 Benzo[f]quinoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3372
16.1.7.10 Carbazole. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3375
16.1.7.11 Benzo[c,g]carbazole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3378
16.1.7.12 Acridine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3380
16.1.8 Sulfur compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3383
16.1.8.1 Carbon disulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3383
16.1.8.2 Dimethyl sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3386
16.1.8.3 Dimethyl disulfide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3391
16.1.8.4 Dimethyl sulfoxide (DMSO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3394
16.1.8.5 Dimethyl sulfate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3397
16.1.8.6 Methanethiol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3399
16.1.8.7 Ethanethiol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3402
16.1.8.8 1-Propanethiol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3406
16.1.8.9 1-Butanethiol (Butyl mercaptan) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3409
16.1.8.10 Benzenethiol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3412
16.1.8.11 Thiophene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3415
16.1.8.12 Benzo[b]thiophene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3419
16.1.8.13 Dibenzothiophene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3421
16.1.8.14 Thiourea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3423
16.1.8.15 Thioacetamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3425
16.2 Summary Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3427
16.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3438
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3197
16.1 LIST OF CHEMICALS AND DATA COMPILATIONS
16.1.1 NITRILES (ORGANIC CYANIDES)
16.1.1.1 Acetonitrile
Common Name: Acetonitrile
Synonym: cyanomethane, ethanenitrile, methyl cyanide
Chemical Name: acetonitrile
CAS Registry No: 75-05-8
Molecular Formula: C2H3N, CH3CN
Molecular Weight: 41.052
Melting Point (°C):
–43.82 (Lide 2003)
Boiling Point (°C):
81.65 (Lide 2003)
Density (g/cm3 at 20°C):
0.7857 (Dreisbach 1961; Weast 1982–83; Dean 1985)
0.7803 (25°C, Dreisbach 1961)
Molar Volume (cm3/mol):
52.7 (calculated-density, Rohrschneider 1973)
57.4 (exptl. at normal bp, Lee et al. 1972)
56.3 (calculated-Le Bas method at normal boiling point)
Dissociation Constant, pK:
29.1 (pKa, Riddick et al. 1986; Howard 1993)
32.2 (pKs, Riddick et al. 1986)
–10.12 (pKBH + , Riddick et al. 1986)
Enthalpy of Vaporization, .HV (kJ/mol):
35.01, 31.51 (25°C, bp, Dreisbach 1961)
32.94, 29.82 (25°C, bp, Riddick et al. 1986)
Enthalpy of Fusion, .Hfus (kJ/mol):
8.167 (Riddick et al. 1986)
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C):
> 3.1 . 106 (Booth & Everson 1948)
miscible (Dean 1985; Riddick et al. 1986; Yaws et al. 1990; Howard 1993)
Vapor Pressure (Pa at 25°C or as indicated and reported temperature dependence equations. Additional data at other
temperatures designated * are compiled at the end of this section):
11870* (interpolated-regression of tabulated data, temp range –47–81.8°C, Stull 1947)
log (P/mmHg) = 7.12257 – 1315.2/(230 + t/°C), (Antoine eq., Dreisbach & Martin 1949)
11240 (calculated by formula, Dreisbach 1961)
log (P/mmHg) = 7.07354 – 1279.2/(224.0 + t/°C), temp range 5–119°C, (Antoine eq. for liquid state, Dreisbach
1961)
12156* (25.56°C, measured range 7.3–27.38°C, Putnam et al. 1965)
log (P/mmHg) = 7.89511 – 1773.06/(T/K); temp range 280–300.5 K (Antoine eq., Putnam et al. 1965)
11510 (Hoy 1970)
24459* (41.82°C, ebulliometry, measured range 41–82°C, Meyer et al. 1971)
log (P/mmHg) = 6.23655 – 1397.9228/(239.275 + t/°C); temp range 41–82°C (ebulliometry, Meyer et al. 1971)
log (P/mmHg) = [–0.2185 . 8173.2/(T/K)] + 7.938662; temp range: –47.0 to 81.8°C, (Antoine eq., Weast
1972–73)
11919* (25.3°C, measured range 15.1–89.2°C, Dojcanske & Heinrich 1974)
N
© 2006 by Taylor & Francis Group, LLC
3198 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
8306* (saturated-vapor volume, extrapolated from fitted Antoine eq., Mousa 1981)
log (P/kPa) = 6.4914 – 1420.8649/(T/K – 42.15); temp range 438.9–530.1 K (ebulliometry, Mousa 1981)
9864, 15330 (20°C, 30°C, Verschueren 1983)
11790, 11830 (interpolated values-Antoine equations, Boublik et al. 1984)
log (P/kPa) = 6.39532 – 1420.682/(241.852 + t/°C), temp range: 15.1–89.2°C (Antoine eq. from reported exptl.
data, Boublik et al. 1984)
log (P/kPa) = 7.54606 – 2093.145/(298.369 + t/°C), temp range: 7.26–27.4°C (Antoine eq. from reported exptl.
data, Boublik et al. 1984)
12310 (calculated-Antoine eq., Dean 1985, 1992)
log (P/mmHg) = 7.11988 – 1314.4/(230 + t/°C), temp range: liquid (Antoine eq., Dean 1985, 1992)
11840 (Riddick et al. 1986; Howard et al. 1986; quoted, Banerjee et al. 1990; Howard 1993)
log (P/kPa) = 6.24747 – 1315.2/(230.0 + t/°C), temp range not specified (Antoine eq., Riddick et al. 1986)
11800 (extrapolated-Antoine eq., Stephenson & Malanowski 1987)
log (PL/kPa) = 6.34522 – 1388.446/(–34.856 + T/K), temp range: 314–355 K, (Antoine eq., Stephenson &
Malanowski 1987)
11840 (selected, Riddick et al. 1986)
log (P/kPa) = 6.24724 – 1315.2/(230 + t/°C), temp range not specified (Antoine eq., Riddick et al. 1986)
log (P/mmHg) = 23.1953 – 2.3389 . 103/(T/K) –5.4954·log (T/K) + 7.9894 . 10–10 · (T/K) + 2.3293 . 10–6 ·
(T/K)2; temp range 229–546 K (vapor pressure eq., Yaws 1994)
10604* (22.634°C, comparative ebulliometry, measured range 278–373 K, Ewing & Sanchez Ochoa 2004)
ln (P/kPa) = 14.7340 – 3268.53/(T/K – 31.615), for temp range 290–362 K (comparative ebulliometry, Ewing
& Sanchez Ochoa 2004)
Henry’s Law Constant (Pa·m3/mol at 25°C or as indicated and reported temperature dependence equations. Additional
data at other temperatures designated* are compiled at the end of this section):
3.50, 2.78 (exptl., calculated-bond contribution, Hine & Mookerjee 1975)
2.07* (headspace-GC, measured range 0–25°C, Snider & Dawson 1985)
2.033 (computed-vapor-liquid equilibrium VLE data, Yaws et al. 1991)
1.474* (20°C, headspace-GC, measured range 6.0–30°C, Benkelberg et al. 1995)
1.474, 1.477, 1.685 (20°C, headspace-GC, deionized water, rain water, artificial seawater, Benkelberg et al. 1995)
ln (kH/atm) = (13.8 ± 0.3) – (4106 ± 101)/T/K), temp range: 6–30°C (headspace-GC measurement, Benkelberg
et al. 1995)
1.55 (20°C, selected from literature experimentally measured data, Staudinger & Roberts 2001)
log KAW = 2.353 – 1627/(T/K) (van’t Hoff eq. derived from literature data, Staudinger & Roberts 2001)
2.05 (Ostwald concentration coefficient-concn ratio-GC/FID, Bebahani et al. 2002)
Octanol/Water Partition Coefficient, log KOW:
–0.34 (shake flask-GC, Hansch & Anderson 1967; Leo et al. 1969, 1971; Hansch & Leo 1985)
–0.54 (shake flask-GC, Tanii & Hashimoto 1984)
–0.34 (recommended, Sangster 1989, 1993)
–0.34 (recommended, Hansch et al. 1995)
Octanol/Air Partition Coefficient, log KOA:
2.31 (head-space GC, Abraham et al. 2001)
Bioconcentration Factor, log BCF:
–0.523 (estimated-KOW as per regression eq of Bysshe 1982, Howard 1993)
Sorption Partition Coefficient, log KOC:
–0.523 (soil, estimated-KOW, Lyman et al. 1982; quoted, Howard 1993)
–0.714 (calculated-KOW, Kollig 1993)
Environmental Fate Rate Constants, k, or Half-Lives, t.:
Volatilization: t. ~ 21 h from a model river of 1-m deep flowing at 1 m/s with a wind velocity of 3 m/s based
on Henry’s law constant (Lyman et al. 1982; quoted, Howard 1993)
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3199
Photolysis:
Oxidation: rate constant k, for gas-phase second order rate constants, kOH for reaction with OH radical, kNO3
with NO3 radical and kO3 with O3 or as indicated, *data at other temperatures and/or the Arrhenius expression
see reference:
photooxidation t. = 314 – 12559 yr in water, based on measured rate data for reaction with hydroxyl radical
in aqueous solution (Dorfman & Adams 1973; Howard et al. 1991)
kOH* = (4.94 ± 0.6) . 10–14 cm3 molecule–1 s–1 at 297.2 K, measured range 297–424 K (flash photolysisresonance
fluorescence, Harris et al. 1981; quoted, Howard 1993)
kOH* = (1.94 ± 0.37) . 10–14 cm3 molecule–1 s–1 at 298 K, measured range 250–363 K (flash photolysisresonance
fluorescence, Kurylo & Knable 1984)
kOH* = (2.1 ± 0.3) . 10–14 cm3 molecule–1 s–1 at 295 K, measured range 295–393 K (discharge flow-EPR,
Poulet et al. 1984)
kOH(exptl) = 2.1 . 10–14 cm3 molecule–1 s–1, kOH(calc) = 2.0 . 10–14 cm3 molecule–1 s–1 at 298 K (Atkinson
1985)
kOH = 3 . 10–14 cm3 molecule–1 s–1 (Atkinson 1985; quoted, Howard et al. 1991; Howard 1993)
kOH = 1.90 . 10–14 cm3 molecule–1 s–1 and k(soln) = 3.70 . 10–14 cm3 molecule–1 s–1 for the solution-phase
reaction with hydroxyl radical in aqueous solution (Wallington et al. 1988)
kOH* = 2.14 . 10–14 cm3 molecule–1 s–1 at 298 K (recommended, Atkinson 1989)
Hydrolysis:
k = 5.8 . 10–3 M–1 h–1 at pH 7 and 25°C with t. > 150000 yr (Ellington et al. 1987)
kO3(aq.) . 6 . 10–5 M–1 s–1 for direct reaction with ozone in water at pH 2 and 22°C, with t. . 18 yr at pH
7 (Yao & Haag 1991).
Biodegradation: t.(aq. aerobic) = 168 – 672 h, based on aerobic river die-away test data (Ludzack et al. 1958;
quoted, Howard et al. 1991); t.(aq. anaerobic) = 672 – 2688 h, based on estimated aqueous aerobic
biodegradation half-life (Howard et al. 1991).
Biotransformation:
Bioconcentration, Uptake (k1) and Elimination (k2) Rate Constants:
Half-Lives in the Environment:
Air: photooxidation t. = 1299 – 12991 h, based on measured rate constant k = 3 . 10–14 cm3 molecule–1 s–1 for
the vapor phase reaction with hydroxyl radical in air (Atkinson 1985; quoted, Howard et al. 1991; Howard
1993);
atmospheric transformation lifetime was estimated to be > 5 d (Kelly et al. 1994).
Surface water: t. = 168 – 672 h, based on aerobic river die-away test data (Howard et al. 1991);
photooxidation t. = 314 – 12559 yr, based on measured rate data for reaction with hydroxyl radical in
aqueous solution (Dorfman & Adams 1973; Howard et al. 1991);
t. . 18 yr for direct reaction with ozone in water at pH 7 and 22°C (Yao & Haag 1991).
Groundwater: t. = 336 – 8640 h, based on estimated aqueous aerobic biodegradation half-life (Howard et al.
1991).
Sediment:
Soil: t. = 168 – 672 h, based on estimated aqueous aerobic biodegradation half-life (Howard et al. 1991).
Biota:
TABLE 16.1.1.1.1
Reported vapor pressures of acetonitrile at various temperatures and the coefficients for the vapor pressure
equations
log P = A – B/(T/K) (1) ln P = A – B/(T/K) (1a)
log P = A – B/(C + t/°C) (2) ln P = A – B/(C + t/°C) (2a)
log P = A – B/(C + T/K) (3)
log P = A – B/(T/K) – C·log (T/K) (4)
(Continued)
© 2006 by Taylor & Francis Group, LLC
3200 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
TABLE 16.1.1.1.1 (Continued)
1.
Stull 1947 Putnam et al. 1965 Meyer et al. 1971 Dojcanske & Heinrich 1974
summary of literature data manometer ebulliometry in Boublik et al. 1984
t/°C P/Pa t/°C P/Pa t/°C P/Pa t/°C P/Pa
–47.0 133.3 7.259 4997 41.82 24459 15.1 7359
–26.6 666.6 10.47 5861 46.09 29026 20.1 9413
–16.3 1333 13.791 6914 46.11 29032 25.3 11919
–5.0 2666 18.701 8809 50.36 34288 30.7 15252
7.7 5333 21.905 10244 55.37 41393 35 18292
15.9 7999 23.401 11031 60.64 50155 39.95 22465
27 13332 25.563 12156 65.91 60390 40 22625
43.7 26664 27.38 13187 70.74 71145 44.9 27638
62.5 53329 76.31 85512 50.1 33797
81.8 101325 eq. 1 P/mmHg 81.87 101990 54.9 40517
A 7.89511 81.89 102010 60 49022
mp/°C –41.0 B 1773.06 64.4 57182
bp/°C 81.66 64.95 58102
eq. 2 P/mmHg 70 68967
A 6.23655 73.05 76713
B 1397.923 75.1 81380
C 239.275 77.2 87952
81.1 99431
85.2 112364
88.2 123189
89.2 124776
2.
Mousa 1981 Ewing & Sanchez Ochoa 2004
ebulliometry-pressure gauge comparative ebulliometry
T/K P/kPa t/°C P/Pa t/°C P/kPa
set A set B
438.9 784.4 4.772 4323# 81.4 100.745
440.9 842.8 5.475 4490# 87.792 122.631
442.6 862.3 8.417 5247# 98.589 168.122
444.5 876.9 12.226 6385# 105.665 204.592
447.9 960.3 14.517 7165# 110.961 235.792
450.5 999.2 17.497 8296 121.144 306.279
455.7 1116.5 19.596 9182 132.086 399.5
460.2 1234.6 22.634 10604 142.063 502.665
505.3 2604.9 27.674 13366 150.533 605.601
508.1 1704.6 30.661 15271 157.974 708.993
512.1 1924.0 36.486 19639 164.152 804.861
519.7 3243.3 42.283 24972 170.346 910.819
521.6 3303.1 47.968 31311 176.446 1025.47
524.8 3482.8 51.872 36387 182.586 1151.97
530.1 3722.1 58.125 45907 188.724 1290.2
63.263 55169 195.22 1450.28
bp/K 354.8 68.029 65092 200.902 1602.63
72.425 75440 206.004 1749.88
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3201
TABLE 16.1.1.1.1 (Continued)
Mousa 1981 Ewing & Sanchez Ochoa 2004
ebulliometry-pressure gauge comparative ebulliometry
T/K P/kPa t/°C P/Pa t/°C P/kPa
eq.3 P/kPa 76.178 85311 211.619 2110.77
A 6.4914 79.929 95589 217.22 2303.51
B 1420.8649 81.515 101120 222.602 2523.66
C –42.15 84.406 110614 228.33 2747.95
88.462 125129 233.771 2999.22
95.816 155329 339.66 3254.08
100.02 175036 244.858 3512.89
254.64 3760.37
for temp range 290–373 K 258.929 4001.46
eq. 2a P/mmHg 261.882 4174.61
A 14.734
B 3268.53 data fitted to Wagner eq.
C –31.615 for temp range 354.5–535 K
# data not used in regression
FIGURE 16.1.1.1.1 Logarithm of vapor pressure versus reciprocal temperature for acetonitrile.
Acetonitrile: vapor pressure vs. 1/T
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0.0018 0.0022 0.0026 0.003 0.0034 0.0038 0.0042 0.0046
1/(T/K)
P( gol
S
) aP/
experimental data
Stull 1947
b.p. = 81.65 °C m.p. = -43.82 °C
© 2006 by Taylor & Francis Group, LLC
3202 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
TABLE 16.1.1.1.2
Reported Henry’s law constants of acetonitrile at various temperatures and temperature dependence
equations
ln KAW = A – B/(T/K) (1) log KAW = A – B/(T/K) (1a)
ln (1/KAW) = A – B/(T/K) (2) log (1/KAW) = A – B/(T/K) (2a)
ln (kH/atm) = A – B/(T/K) (3)
ln [H/(Pa m3/mol)] = A – B/(T/K) (4) ln [H/(atm·m3/mol)] = A – B/(T/K) (4a)
KAW = A – B·(T/K) + C·(T/K)2 (5)
Snider & Dawson 1985 Benkelberg et al. 1995
gas stripping-GC equil. vapor phase concn-GC
t/°C H/(Pa m3/mol) t/°C H/(Pa m3/mol)
deionized water
0 0.614 6 0.72
25 2.066 10 1.0706
20 1.474
enthalpy of transfer: 30 2.356
.H/(kJ mol–1) = 30.54 rain water
20 1.477
artificial
20 1.685
eq. 3 H/atm
A 13.8 ± 0.3
B 4106 ± 101
FIGURE 16.1.1.1.2 Logarithm of Henry’s law constant versus reciprocal temperature for acetonitrile.
Acetonitrile: Henry's law constant vs. 1/T
-2.0
-1.0
0.0
1.0
2.0
0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036 0.0037 0.0038
1/(T/K)
m. aP( / H nl
3
) l om
/
Snider & Dawson 1985
Benkelberg et al. 1995 (in deionized water)
Benkelberg et al. 1995 (in rain water)
Hine & Mookerjee 1975
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3203
16.1.1.2 Propionitrile
Common Name: Propionitrile
Synonym: propanenitrile, ethyl cyanide, cyanoethane, propyl nitrile
Chemical Name: propionitrile
CAS Registry No: 107-12-0
Molecular Formula: C3H5N, CH3CH2CN
Molecular Weight: 55.079
Melting Point (°C):
–92.78 (Lide 2003)
Boiling Point (°C):
97.14 (Lide 2003)
Density (g/cm3 at 20°C):
0.7818 (Weast 1982–83; Dean 1985)
0.78182, 0.77682 (20°C, 25°C, Riddick et al. 1986)
Molar Volume (cm3/mol):
70.4 (calculated-density, Taft et al. 1985; Leahy 1986; Kamlet et al. 1986, 1987)
78.5 (calculated-Le Bas method at normal boiling point)
Dissociation Constant:
33.54 (pKs, Riddick et al. 1986)
Enthalpy of Vaporization, .Hvap, (kJ/mol):
37.41, 32.77 (25°C, bp, Dreisbach 1961)
36.03, 30.96 (25°C, bp, Riddick et al. 1986)
Enthalpy of Fusion, .Hfus (kJ/mol):
5.045 (Riddick et al. 1986)
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C or as indicated. Additional data at other temperatures designated * are
compiled at the end of this section):
104950 (Seidell 1941)
105200 (Hansch et al. 1968)
103000 (Dean 1985; Riddick et al. 1986; Howard 1990)
55000, 65000 (20°C, 30°C, shake flask-GC, measured range 0–90°C, Stephenson 1994)
Vapor Pressure (Pa at 25°C or as indicated and reported temperature dependence equations. Additional data at other
temperatures designated * are compiled at the end of this section):
6005* (interpolated-regression of tabulated data, temp range –35–97.1°C, Stull 1947)
10114* (35.5°C, ebulliometry, measured range 35.5–97.35°C, Dreisbach & Shrader 1949)
log (P/mmHg) = 7.15217 – 1398.2/(230 + t/°C); temp range 35.5–97.35°C, (Antoine eq., Dreisbach & Martin
1949)
5333* (22.05°C, measured range –84.66–22.05°C, Milazzo 1956)
5950 (calculated by formula, Dreisbach 1961)
log (P/mmHg) = 7.05846 – 1327.9/(221.0 + t/°C), temp range: 17–137°C, (Antoine eq. for liquid state, Dreisbach
1961)
log (P/mmHg) = [–0.2185 . 8769.0/(T/K)] + 8.079473; temp range: –35 to 97.1°C, (Antoine eq., Weast 1972–73)
6140 (22.05°C, quoted exptl., Boublik et al. 1973, 1984)
6163, 6143 (extrapolated values-Antoine eq., Boublik et al. 1984)
log (P/kPa) = 5.89149 – 1181.562/(206.603 + t/°C), temp range: 35.5–97.39°C (Antoine eq. from reported exptl.
data, Boublik et al. 1984)
log (P/kPa) = 4.43918 – 677.415/(160.551 + t/°C), temp range: –84.7 to 22.05°C (Antoine eq. from reported
exptl. data, Boublik et al. 1984)
N
© 2006 by Taylor & Francis Group, LLC
3204 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
6140 (extrapolated-Antoine eq., Dean 1985, 1992)
log (P/mmHg) = 5.2782 – 665.52/(159.0 + t/°C), temp range: –84 to 22°C (Antoine eq., Dean 1985, 1992)
5950 (selected, Riddick et al. 1986)
log (P/kPa) = 6.27702 – 1398.2/(230 + t/°C), temp range not specified (Antoine eq., Riddick et al. 1986)
log (P/kPa) = 7.15190 – 1894.10/(T/K); temp range: 9–25°C, (Antoine eq., Riddick et al. 1986)
6306 (calculated-Antoine eq., Stephenson & Malanowski 1987)
log (PL/kPa) = 7.395 – 3213/(T/K), temp range: 357–413 K, (Antoine eq.-I, Stephenson & Malanowski 1987)
log (PL/kPa) = 10.31055 – 3994.667/(T/K), temp range: 373–413 K, (Antoine eq.-II, Stephenson & Malanowski
1987)
log (P/mmHg) = 33.7908 – 2.9113 . 103/(T/K) – 9.1506·log (T/K) + 1.1173 . 10–11·(T/K) + 3.2756 . 10–6·(T/K)2;
temp range 180–564 K (vapor pressure eq., Yaws 1994)
Henry’s Law Constant (Pa·m3/mol at 25°C):
3.800 (partial pressure, Butler & Ramchandani 1935)
3.748 (partial vapor pressure-GC, Buttery et al. 1969)
3.752, 3.752, 4.114 (exptl., calculated-group contribution, calculated-bond contribution, Hine & Mookerjee 1975)
5.947 (Howard 1990)
Octanol/Water Partition Coefficient, log KOW:
0.041 (shake flask, Collander 1951)
0.16 (shake flask-GC, Hansch & Anderson 1967; Hansch et al. 1968)
– 0.10 (shake flask-GC, Tanii & Hashimoto 1984)
0.16 (recommended, Sangster 1989, 1993)
0.16 (recommended, Hansch et al. 1995)
Octanol/Air Partition Coefficient, log KOA:
2.69 (head-space GC, Abraham et al. 2001)
Bioconcentration Factor, log BCF:
– 0.108 (estimated-KOW, Lyman et al. 1982; quoted, Howard 1990)
Sorption Partition Coefficient, log KOC:
0.079 (soil, estimated-KOW, Lyman et al. 1982; quoted, Howard 1990)
Environmental Fate Rate Constants, k, or Half-Lives, t.:
Volatilization: using Henry’s law constant, t. = 13.3 h was estimated for a model river 1 m deep flowing 1 m/s
with wind speed 3 m/s (Lyman et al. 1982; quoted, Howard 1990).
Photolysis:
Oxidation: rate constant k, for gas-phase second order rate constants, kOH for reaction with OH radical, kNO3
with NO3 radical and kO3 with O3 or as indicated, *data at other temperatures and/or the Arrhenius expression
see reference:
kOH* = (1.94 ± 0.20) . 10–13 cm3 molecule–1 s–1 at 298.2 K, measured range 298–423 K (flash photolysisresonance
fluorescence, Harris et al. 1981)
kOH = 1.9 . 10–13 cm3 molecule–1 s–1 at 298 K (Atkinson 1985)
kOH = 1.94 . 10–13 cm3 molecule–1 s–1 at 298.2 K, k(soln) = 1.60 . 10–13 cm3 molecule–1 s–1 for the solutionphase
reaction with hydroxyl radical in aqueous solution (Wallington et al. 1988)
photooxidation t. = 83 d in air, based on experimental rate constant assuming t. = 12 h of sunlight for the
vapor-phase reaction with hydroxyl radical in air and t. > 100 d for the reaction with ozone in the
atmosphere (Howard 1990)
kOH = 0.194 . 10–12 cm3 molecule–1 s–1 at 298.2 K (review, Atkinson 1989)
Hydrolysis:
Biodegradation:
Biotransformation:
Bioconcentration, Uptake (k1) and Elimination (k2) Rate Constants:
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3205
Half-Lives in the Environment:
Air: t. = 83 d, based on experimental rate constant assuming 12 h of sunlight for the vapor-phase reaction with
hydroxyl radical in air and t. > 100 d for the reaction with ozone in the atmosphere (Harris et al. 1981;
quoted, Howard 1990).
TABLE 16.1.1.2.1
Reported aqueous solubilities and vapor pressures of propionitrile at various temperatures
log P = A – B/(T/K) (1) ln P = A – B/(T/K) (1a)
log P = A – B/(C + t/°C) (2) ln P = A – B/(C + t/°C) (2a)
log P = A – B/(C + T/K) (3)
log P = A – B/(T/K) – C·log (T/K) (4)
Aqueous solubility Vapor pressure
Stephenson 1994 Stull 1947 Dreisbach & Shrader 1949 Milazzo 1956
shake flask-GC summary of literature data ebulliometry
t/°C S/g·m–3 t/°C P/Pa t/°C P/Pa t/°C P/Pa
0 62000 –35.0 133.3 35.5 10114 –84.66 1
20 55000 –13.8 666.6 43.76 16500 –77.01 2
30 65000 –3.0 1333 70.45 42066 –67.42 6
40 79000 8.8 2666 84.44 67661 –65.49 7
50 94000 22 5333 97.35 101325 –59.72 13
60 98000 30.1 7999 –52.96 17
70 134000 41.4 13332 –46.19 49
80 156000 58.2 26664 –34.95 133
90 195000 77.7 53329 –22.85 356
97.1 101325 –13.08 707
–2.95 1347
mp/°C –91.9 6.36 2400
16.42 4146
22.05 5333
FIGURE 16.1.1.2.1 Logarithm of mole fraction solubility (ln x) versus reciprocal temperature for propionitrile.
Propionitrile: solubility vs. 1/T
-4.5
-4.0
-3.5
-3.0
-2.5
0.0026 0.0028 0.003 0.0032 0.0034 0.0036 0.0038
1/(T/K)
x
nl
Stephenson 1994
© 2006 by Taylor & Francis Group, LLC
3206 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
FIGURE 16.1.1.2.2 Logarithm of vapor pressure versus reciprocal temperature for propionitrile.
Propionitrile: vapor pressure vs. 1/T
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
0.0026 0.003 0.0034 0.0038 0.0042 0.0046 0.005 0.0054 0.0058
1/(T/K)
P( gol
S
) aP/
Dreisbach & Shrader 1949
Milazzo 1956
Stull 1947
b.p. = 97.14 °C m.p. = -92.78 °C
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3207
16.1.1.3 Butyronitrile
Common Name: n-Butyronitrile
Synonym: butanenitrile
Chemical Name: butyronitrile
CAS Registry No: 109-74-0
Molecular Formula: C4H7N, CH3CH2CH2CN
Molecular Weight: 69.106
Melting Point (°C):
–111.9 (Lide 2003)
Boiling Point (°C):
117.6 (Lide 2003)
Density (g/cm3):
0.7911, 0.7865 (20°C, 25°C, Riddick et al. 1986)
Dissociation Constant, pKa:
Molar Volume (cm3/mol):
88.4 (30°C, Stephenson & Malanowski 1987)
100.7 (calculated-Le Bas method at normal boiling point)
Enthalpy of Vaporization, .HV (kJ/mol):
39.33, 34.43 (25°C, bp, Riddick et al. 1986)
Enthalpy of Sublimation, .Hsubl (kJ/mol):
Enthalpy of Fusion, .Hfus (kJ/mol):
5.021 (Riddick et al. 1986)
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C or as indicated. Other data at other temperatures designated * are compiled
at the end of this section):
33000 (selected, Riddick et al. 1986)
33500* (20°C, shake flask-GC/TC, measured range 0–90°C, Stephenson 1994)
Vapor Pressure (Pa at 25°C or as indicated and the reported temperature dependence equations. Additional data at
other temperatures designated * are compiled at the end of this section):
1333* (25.7°C, summary of literature data, temp range –20 to 117.5°C, Stull 1947)
3592* (30.64°C, ebulliometry, measured range 30.64–120.223°C, Meyer et al. 1971)
log (P/mmHg) = 6.771124 – 1444.5851/(t/°C + 223.275); temp range 30.64–120.223°C (Antoine eq.,
ebulliometric measurements, Meyer et al. 1971)
13831* (59.807°C, ebulliometry, measured range 59.807–127.707°C, Meyer & Hotz 1976)
2546 (selected, Riddick et al. 1986)
log (P/kPa) = 6.25390 – 1452.076/(t/°C + 224.1855); temp range not specified (Riddick et al. 1986)
log (PL/kPa) = 6.25397 – 1452.076/(–46.9645 + T/K); temp range 332–401 K (Antoine eq., Stephenson &
Malanowski 1987)
log (P/mmHg) = 4.8780 – 2.5505 . 103/(T/K) + 3.6306·log (T/K) – 1.663 . 10–2·(T/K) + 1.0604 . 10–5·(T/K)2;
temp range 161–582 K (vapor pressure eq., Yaws 1994)
Henry’s Law Constant (Pa m3/mol at 25°C):
Octanol/Water Partition Coefficient, log KOW:
0.53 (shake flask-GC, Tanii & Hashimoto 1984)
0.53 (recommended, Sangster 1993; Hansch et al. 1995)
N
© 2006 by Taylor & Francis Group, LLC
3208 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
Bioconcentration Factor, log BCF or log KB:
Sorption Partition Coefficient, log KOC:
TABLE 16.1.1.3.1
Reported aqueous solubilities and vapor pressures of butyronitrile at various temperatures
log P = A – B/(T/K) (1) ln P = A – B/(T/K) (1a)
log P = A – B/(C + t/°C) (2) ln P = A – B/(C + t/°C) (2a)
log P = A – B/(C + T/K) (3)
log P = A – B/(T/K) – C·log (T/K) (4)
Aqueous solubility Vapor pressure
Stephenson 1994 Stull 1947 Meyer et al. 1971 Meyer & Hotz 1976
shake flask-GC summary of literature data ebulliometry ebulliometry
t/°C S/g·m–3 t/°C P/Pa t/°C P/Pa t/°C P/Pa
0 37500 –20.0 133.3 30.64 3592 59.807 13831
20 33500 2.10 666.6 39.03 5459 65.615 17513
30 33100 13.4 1333 49.913 9041 71.638 22151
40 32500 25.7 2666 59.226 13527 77.023 27111
50 32300 38.4 5333 67.536 18888 83.599 34366
60 32100 47.3 7999 77.313 27448 89.462 42109
70 31900 59.0 13332 86.71 39316 96.022 52382
80 34000 76.7 26664 93.675 48525 102.279 63984
90 36100 96.8 53329 100.638 60811 109.175 79081
117.5 101325 100.701 60928 115.651 95737
107.041 74214 121.838 114148
mp/°C 112.04 88451 127.707 134135
117.254 100344
120.223 109170
bp/°C 117.583
log P = A – B/(C + t/°C)
P/mmHg
A 6.771124
B 1444.5851
C 223.275
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3209
FIGURE 16.1.1.3.1 Logarithm of mole fraction solubility (ln x) versus reciprocal temperature for butyronitrile.
FIGURE 16.1.1.3.2 Logarithm of vapor pressure versus reciprocal temperature for butyronitrile.
Butyronitrile: solubility vs. 1/T
-5.5
-5.0
-4.5
-4.0
-3.5
0.0026 0.0028 0.003 0.0032 0.0034 0.0036 0.0038
1/(T/K)
x nl
Stephenson 1994
Butyronitrile: vapor pressure vs. 1/T
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0.0022 0.0026 0.003 0.0034 0.0038 0.0042
1/(T/K)
P
( gol
S
) aP/
Meyer et al. 1971
Meyer & Hotz 1976
Stull 1947
b.p. = 117.6 °C
© 2006 by Taylor & Francis Group, LLC
3210 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
16.1.1.4 Acrylonitrile (2-Propenenitrile)
Common Name: Acrylonitrile
Synonym: cyanoethylene, propenenitrile, 2-propenenitrile, vinyl cyanide
Chemical Name: acrylonitrile, cyanoethylene
CAS Registry No: 107-13-1
Molecular Formula: C3H3N, CH2=CHCN
Molecular Weight: 53.063
Melting Point (°C):
–83.48 (Lide 2003)
Boiling Point (°C):
77.30 (Riddick et al. 1986; Howard 1989; Lide 2003)
Density (g/cm3 at 20°C):
0.8060, 0.8004 (20°C, 25°C, Riddick et al. 1986)
Molar Volume (cm3/mol):
65.8 (20°C, calculated-density)
71.1 (calculated-Le Bas method at normal boiling point)
Dissociation Constant, pKa:
Enthalpy of Fusion, .Hfus (kJ/mol):
6.230 (Riddick et al. 1986)
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C or as indicated. Additional data at other temperatures designated * are
compiled at the end of this section):
79000 (Klein et al. 1957)
75000 (Gunther et al. 1968)
73500 (20°C, Windholz 1976)
73240 (shake flask-LSC, Veith et al. 1980)
7.35 wt%* (20°C, Kirk-Othmer Encyclopedia 3rd ed., measured range 0–60°C, quoted, Basu et al. 1983)
73500 (20°C, Riddick et al. 1986)
69000*, 66400 (20°C, 30°C, shake flask-GC, measured range 0–70°C, Stephenson 1994)
Vapor Pressure (Pa at 25°C or as indicated and reported temperature dependence equations. Additional data at other
temperatures designated * are compiled at the end of this section):
14340* (interpolated-regression of tabulated data, temp range –51 to 78.5°C, Stull 1947)
11732* (20°C, temp range 20–77°C, Gudkov et al. 1964; quoted, Boublik et al. 1984)
14100 (Hoy 1970)
log (P/mmHg) = [–0.2185 . 7941.4/(T/K)] + 7.851016; temp range: –51 to 78.5°C, (Antoine eq., Weast 1972–73)
14720 (extrapolated-Antoine eq., Boublik et al. 1984)
log (P/kPa) = 4.77668 – 649.583/(155.006 + t/°C), temp range 20–70°C (Antoine eq. from reported exptl. data,
Boublik et al. 1984)
14370 (Daubert & Danner 1985)
15240 (calculated-Antoine eq., Dean 1985, 1992)
log (P/mmHg) = 7.03855 – 1232.53/(222.47 + t/°C), temp range –20 to 140°C (Antoine eq., Dean 1985, 1992)
11000 (20°C, Riddick et al. 1986)
log (P/kPa) = 6.643 – 11644.7/(T/K), temp range not specified (Antoine eq., Riddick et al. 1986)
14560 (interpolated-Antoine eq.-II, Stephenson & Malanowski 1987)
log (PL/kPa) = 6.12021 – 1288.9/(–38.74 + T/K); temp range 257–352 K (Antoine eq.-I, Stephenson &
Malanowski 1987)
log (PL/kPa) = 6.4811 – 1518.381/(–12.003 + T/K); temp range 283–343 K (Antoine eq.-II, Stephenson &
Malanowski 1987)
N
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3211
15600 (calculated-solvatochromic parameters, Banerjee et al. 1990)
log (P/mmHg) = 35.921 – 2.7763 . 103/(T/K) – 10.101·log (T/K) – 3.1547 . 10–10·(T/K) + 4.7299 . 10–6·(T/K)2;
temp range 190–535 K (vapor pressure eq., Yaws 1994)
Henry’s Law Constant (Pa·m3/mol at 25°C):
11.14 (Bocek 1976; quoted, Basu et al. 1983; Howard 1989)
8.918 (calculated-P/C, Mabey et al. 1982)
9.420 (quoted, WERL Treatability Database, Ryan et al. 1988)
Octanol/Water Partition Coefficient, log KOW:
0.25 (shake flask-HPLC, Pratesi et al. 1979)
0.00 (shake flask, Fujisawa & Masuhara 1980, 1981)
0.09 (shake flask-GC, Tanii & Hashimoto 1984)
0.25 (Hansch & Leo 1985)
0.25 (recommended, Sangster 1989)
0.25 (recommended, Hansch et al. 1995)
Octanol/Air Partition Coefficient, log KOA:
Bioconcentration Factor, log BCF:
1.68 (bluegill sunfish, Barrows et al. 1978)
0.00 (estimated-S, Kenaga 1980)
1.68, 0.32 (bluegill sunfish, calculated-KOW, Veith et al. 1980)
0.017 (microorganisms-water, calculated-KOW, Mabey et al. 1982)
Sorption Partition Coefficient, log KOC:
0.954 (soil, calculated-S, Kenaga 1980)
–0.071 (sediment-water, calculated-KOW, Mabey et al. 1982)
1.101, 1.006; 1.09 (Captina silt loam, McLaurin sandy loam; weighted mean, batch equilibrium-sorption isotherm,
Walton et al. 1992)
–0.0899 (calculated-KOW, Walton et al. 1992)
–0.0890 (calculated-KOW, Kollig 1993)
Environmental Fate Rate Constants, k, or Half-Lives, t.:
Volatilization: t. = 6, 1.2, 4.8 d in a typical pond, river and lake are 6, 1.2, and 4.8 d, respectively, with the
reaeration for oxygen in typical bodies of water (Lyman et al. 1982; quoted, Howard 1989)
evaporation t. = 795 min from water with an assumed 1-m depth (Basu et. al. 1983).
Photolysis:
Oxidation: rate constant k, for gas-phase second order rate constants, kOH for reaction with OH radical, kNO3
with NO3 radical and kO3 with O3 or as indicated, *data at other temperatures see reference:
k < 1 . 108 M–1 h–1 for singlet oxygen, and 36 M–1 h–1 for peroxy radical at 25°C (Mabey et al. 1982)
t. = 4.0 h for photooxidation in the troposphere (Callahan et al. 1979)
kOH = (40.6 ± 4.1) . 10–13 cm3 molecule–1 s–1 at 299 K (flash photolysis-resonance fluorescence technique,
Harris et al. 1981)
kO3 < 1 . 10–19 cm3 molecule–1 s–1 at 296 ± 2 K, and tropospheric lifetimes, . > 115 d and . = 3 d due to
reactions with O3 and OH radical, respectively (Atkinson et al. 1982)
kO3 < 1 . 10–19 cm3 molecule–1 s–1 at 296 ± 2 K (Atkinson et al. 1983; quoted, Atkinson & Carter 1984)
t. = 3.5 d for the reaction with photochemically produced hydroxyl radical by the sunlight (Edney et al.
1983; quoted, Howard 1989)
kOH = 4.8 . 10–12 cm3 molecule–1 s–1 at 298.7 K, and kOH = 3.4 . 10–12 cm3 molecule–1 s–1 at 296 K (review,
flash photolysis-resonance fluorescence technique Atkinson 1985)
photooxidation t. = 3.4–189 h, based on measured rate constant for the reaction with hydroxyl radical in
air (Howard et al. 1991)
kOH = (3.4 – 4.80) . 10–12 cm3 molecule–1 s–1 at 296–298.2 K (review, Atkinson 1989)
© 2006 by Taylor & Francis Group, LLC
3212 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
Hydrolysis: k(acid) = 4.2 . 10–2 M–1 h–1 at pH 5.0 with t. = 188 yr and k(base) = 6.1 . 10–2 M–1 h–1 at pH 9.0
with t. = 13 yr (Ellington et al. 1987; quoted, Howard et al. 1991, Kollig 1993);
t. = 1210 yr at pH 7.0, based on measured acid and base catalyzed hydrolysis constants (Ellington et al.
1987; quoted, Howard et al. 1991)
t. = 69 d at pH 2, t. = 440000 d at pH 7 and t. = 4.7 d at pH 12 in natural waters (Capel & Larson 1995).
Biodegradation: t.(aq. aerobic) = 30–552 h, based on river die-away test data (Going et al. 1979; Ludzack
et al. 1958; quoted, Howard et al. 1991); t.(aq. anaerobic) = 120–2208 h, based on estimated aqueous aerobic
biodegradation half-life (Howard et al. 1991)
14C labeled acrylonitrile at concentrations up to 100 ppm was completely degraded within 2.0 d in a London
soil under aerobic conditions (Donberg et al. 1992)
t.(aerobic) = 1.3 d, t.(anaerobic) = 5 d in natural waters (Capel & Larson 1995)
Biotransformation: k = of 3 . 10–9 mL cell–1 h–1 for bacterial transformation in water (Mabey et al. 1982).
Bioconcentration, Uptake (k1) and Elimination (k2) Rate Constants:
Half-Lives in the Environment:
Air: t. = 4.0 h for photooxidation in the troposphere (Callahan et al. 1979);
t. = 3.5 d for the reaction with photochemically produced hydroxyl radical by the sunlight (Edney et al.
1983; quoted, Howard 1989);
photooxidation t. = 13.4–189 h, based on measured rate constant for the reaction with hydroxyl radicals in
air (Atkinson 1985; quoted, Howard et al. 1991);
atmospheric transformation lifetime was estimated to be 1 – 5 to > 5 d (Kelly et al. 1994).
Surface water: t. = 30–552 h, based on estimated aqueous aerobic biodegradation half-life (Howard et al. 1991)
Biodegradation t.(aerobic) = 100 d, t.(anaerobic) = 400 d; hydrolysis t. = 69 d at pH 2, t. = 440000 d at
pH 7 and t. = 4.7 d at pH 12 in natural waters (Capel & Larson 1995).
Groundwater: t. = 60–1104 h based on estimated aqueous aerobic biodegradation half-life (Howard et al. 1991).
Sediment:
Soil: t. < 10 d in soil (USEPA 1979; quoted, Ryan et al. 1988);
t. = 30–552 h based on estimated aqueous aerobic biodegradation half-life (Howard et al. 1991).
Biota:
TABLE 16.1.1.4.1
Reported aqueous solubilities and vapor pressures of acrylonitrile at various temperatures
Aqueous solubility Vapor pressure
Othmer Encyclopedia Stephenson 1994 Stull 1947 Gudkov et al. 1964
Basu et al. 1983 shake flask-GC summary of literature data in Boublik et al. 1984
t/°C S/g·m–3 t/°C S/g·m–3 t/°C P/Pa t/°C P/Pa
0 72000 0 65800 –51.0 133.3 20 11732
20 73500 10 66800 –30.7 666.6 30 18932
40 79000 20 69000 –20.3 1333 40 27998
60 91000 30 66400 –9.0 2666 50 38530
40 68800 3.8 5333 60 57328
50 73600 11.8 7999 70 78660
60 73900 22.8 13332
70 85600 38.7 26664
58.3 53329
78.5 101325
mp/°C –82.0
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3213
FIGURE 16.1.1.4.1 Logarithm of mole fraction solubility (ln x) versus reciprocal temperature for acrylonitrile.
FIGURE 16.1.1.4.2 Logarithm of vapor pressure versus reciprocal temperature for acrylonitrile.
Acrylonitrile: solubility vs. 1/T
-4.5
-4.0
-3.5
-3.0
-2.5
0.0026 0.0028 0.003 0.0032 0.0034 0.0036 0.0038
1/(T/K)
x nl
Basu et al. 1983
Stephenson 1994
Veith et al. 1980
Acrylonitrile: vapor pressure vs. 1/T
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0.0026 0.003 0.0034 0.0038 0.0042 0.0046 0.005 0.0054
1/(T/K)
P( gol
S
) aP/
Gudkov et al. 1964
Stull 1947
b.p. = 77.3 °C m.p. = -83.48 °C
© 2006 by Taylor & Francis Group, LLC
3214 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
16.1.1.5 Benzonitrile
Common Name: Benzonitrile
Synonym: benzenecarbonitrile, cyanobenzene, phenyl cyanide
Chemical Name: benzonitrile, benzoic acid nitrile
CAS Registry No: 100-47-0
Molecular Formula: C6H5CN
Molecular Weight: 103.122
Melting Point (°C):
–13.99 (Lide 2003)
Boiling Point (°C):
191.1 (Lide 2003)
Density (g/cm3 at 20°C):
1.0006 (25°C, Dean 1985; Riddick et al. 1986)
Molar Volume (cm3/mol):
103.1 (25°C, calculated-density)
107.9 (calculated-Le Bas method at normal boiling point)
Dissociation Constant, pKa:
Enthalpy of Vaporization, .HV (kJ/mol):
55.48, 45.94 (25°C, bp, Riddick et al. 1986)
Enthalpy of Fusion, .Hfus (kJ/mol):
10.88 (Riddick et al. 1986)
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C or as indicated. Additional data at other temperatures designated * are
compiled at the end of this section):
4330 (shake flask-UV, McGowan et al. 1966)
2000 (Dean 1985; Riddick et al. 1986)
10000 (selected, Yaws et al. 1990)
4000* (shake flask-GC/TC, measured range 0–90°C, Stephenson 1994)
Vapor Pressure (Pa at 25°C and reported temperature dependence equations. Additional data at other temperatures
designated * are compiled at the end of this section):
133.3* (38.4°C, static method, measured range 38.4–190.6°C, Kahlbaum 1898)
133.3* (28.2°C, summary of literature data, temp range 28.2–190.6°C, Stull 1947)
log (P/mmHg) = [–0.2185 . 11341.0/(T/K)] + 8.239760; temp range: 28.2–190.6°C (Antoine eq., Weast 1972–73)
78.86 (calculated-Antoine eq., Dean 1985, 1992)
log (P/mmHg) = 6.74631 – 1436.72/(181 + t/°C), temp range: liquid (Antoine eq., Dean 1985, 1992)
100.0 (Riddick et al. 1986)
log (P/kPa) = 5.87121 – 1436.72/(181.0 + t/°C), temp range not specified (Antoine eq., Riddick et al. 1986)
106.0 (extrapolated-Antoine eq., Stephenson & Malanowski 1987)
log (PL/kPa) = 6.79506 – 2066.71/(–32.19 + T/K), temp range 301–464 K (Antoine eq.-I, Stephenson &
Malanowski 1987)
Henry’s Law Constant (Pa·m3/mol at 25°C):
55.32 (computed-vapor-liquid equilibrium VLE data, Yaws et al. 1991)
Octanol/Water Partition Coefficient, log KOW:
1.56 (shake flask-UV spectrophotometry, Fujita et al. 1964; quoted, Leo et al. 1969; Hansch & Leo 1979)
1.56 (shake flask-UV, Holmes & Lough 1976)
N
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3215
1.67 (calculated-fragment const., Rekker 1977)
1.56 (shake flask at pH 7, Unger et al. 1978)
1.66 (RP-HPLC-k. correlation, Miyake & Terada 1982)
1.65 ± 0.01 (HPLC-RV correlation-ALPM, Garst & Wilson 1984)
1.50 (HPLC-k. correlation, Haky & Young 1984)
1.56 (shake flask-GC, Tanii & Hashimoto 1984)
1.56 (RP-HPLC-capacity ratio, Minick et al. 1988)
1.45 (RP-HPLC-RT correlation, ODS column with masking agent, Bechalany et al. 1989)
1.56 (recommended, Sangster 1989, 1993)
1.56 (shake flask-GC, Alcorn et al. 1993)
1.56 (recommended, Hansch et al. 1995)
Octanol/Air Partition Coefficient, log KOA:
4.46 (head-space GC, Abraham et al. 2001)
Bioconcentration Factor, log BCF:
Sorption Partition Coefficient, log KOC:
Environmental Fate Rate Constants, k, or Half-Lives, t.:
Volatilization:
Photolysis:
Oxidation: rate constant k; for gas-phase second order rate constants, kOH for reaction with OH radical, kNO3
with NO3 radical and kO3 with O3 or as indicated, *data at other temperatures see reference:
kOH = 3.3 . 10–13 cm3 molecule–1 s–1 at room temp. (Zetzsch 1982; Atkinson 1989)
kOH(calc) = 4.2 . 10–13 cm3 molecule–1 s–1 at room temp. (Atkinson 1985)
kOH(calc) = 3.9 . 10–13 cm3 molecule–1 s–1 at room temp. (Atkinson et al. 1985)
kOH(calc) = 3.6 . 10–13 cm3 molecule–1 s–1, kOH(obs) = 3.3 . 10–13 cm3 molecule–1 s–1 at room temp. (SAR
structure-activity relationship, Atkinson 1987)
kOH(calc) = 4.1 . 10–13 cm3 molecule–1 s–1 (molecular orbital calculations, Klamt 1993)
Hydrolysis:
Biodegradation:
Biotransformation:
Bioconcentration, Uptake (k1) and Elimination (k2) Rate Constants:
Half-Lives in the Environment:
Surface water: an estimated t. = 1.3 d in Rhine River in case of first order reduction process (Zoeteman et al. 1980)
TABLE 16.1.1.5.1
Reported aqueous solubilities and vapor pressures of butyronitrile at various temperatures
Aqueous solubility Vapor pressure
Stephenson 1994 Kahlbaum 1898* Stull 1947
shake flask-GC static-manometer summary of literature data
t/°C S/g·m–3 t/°C P/Pa t/°C P/Pa t/°C P/Pa
0 3500 38.4 133.3 141.4 26664 28.2 133.3
10 3300 45.3 266.6 155.8 39997 55.3 666.6
20 4000 50.0 400.0 165.8 53329 69.2 1333
40 4500 53.8 533.3 174.4 66661 83.4 2666
50 3800 56.9 666.6 181.6 79993 99.6 5333
60 4200 69.1 1333.2 187.7 93326 109.8 7999
(Continued)
© 2006 by Taylor & Francis Group, LLC
3216 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
TABLE 16.1.1.5.1 (Continued)
Aqueous solubility Vapor pressure
Stephenson 1994 Stull 1947 Meyer et al. 1971 Meyer & Hotz 1976
shake flask-GC summary of literature data ebulliometry ebulliometry
t/°C S/g·m–3 t/°C P/Pa t/°C P/Pa t/°C P/Pa
70 6000 83.0 2666.4 190.6 101325 123.5 13332
80 9500 92.1 3999.7 144.1 26664
90 9100 98.5 5332.9 *complete list see ref. 156.7 53329
103.9 6666.1 190.6 101325
.Hsol/(kJ mol–1) 113.7 9999.2
25 EC 121.3 13332 mp/EC –12.9
FIGURE 16.1.1.5.1 Logarithm of mole fraction solubility (ln x) versus reciprocal temperature for benzonitrile.
Benzonitrile: solubility vs. 1/T
-8.0
-7.5
-7.0
-6.5
-6.0
0.0026 0.0028 0.003 0.0032 0.0034 0.0036 0.0038
1/(T/K)
x n l
Stephenson 1994
McGowan et al. 1966
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3217
FIGURE 16.1.1.5.2 Logarithm of vapor pressure versus reciprocal temperature for benzonitrile.
Benzonitrile: vapor pressure vs. 1/T
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0.0018 0.0022 0.0026 0.003 0.0034 0.0038 0.0042
1/(T/K)
log(PS/Pa)
Kahlbaum 1898
Stull 1947
b.p. = 191.1 °C m.p. = -13.99 °C
© 2006 by Taylor & Francis Group, LLC
3218 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
16.1.2 ALIPHATIC AMINES
16.1.2.1 Dimethylamine
Common Name: Dimethylamine
Synonym: aminomethylmethane, N-methylmethanamine
Chemical Name: aminomethylmethane, dimethylamine
CAS Registry No: 124-40-3
Molecular Formula: C2H7N, CH3NHCH3
Molecular Weight: 45.084
Melting Point (°C):
–92.18 (Lide 2003)
Boiling Point (°C):
6.88 (Lide 2003)
Density (g/cm3 at 20°C):
0.6804 (0°C, Weast 1982–83)
0.6556, 0.6496 (20°C, 25°C, Riddick et al. 1986)
Molar Volume (cm3/mol):
68.8 (20°C, calculated-density)
67.5 (calculated-Le Bas method at normal boiling point)
Dissociation Constant, pKa:
10.732 (Perrin 1965; Weast 1982–83; Howard 1990)
10.77 (protonated cation + 1, Dean 1985)
10.77 (Sangster 1989)
Enthalpy of Vaporization, .HV (kJ/mol):
23.84, 24.61 (25°C, bp, Dreisbach 1961)
23.65, 24.61 (25°C, bp, Riddick et al. 1986)
Enthalpy of Fusion, .Hfus (kJ/mol):
5.941 (Riddick et al. 1986)
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C):
very soluble (Dean 1985)
620000 (selected, Yaws et al. 1990)
miscible (Stephenson 1993b)
Vapor Pressure (Pa at 25°C and reported temperature dependence equations. Additional data at other temperatures
designated * are compiled at the end of this section):
101141* (280.018 K, static method, measured range 201.387–280.018 K, Ashton et al. 1939)
236420* (extrapolated-regression of tabulated data, temp range –87.2 to + 7.4°C, Stull 1947)
196800 (calculated by formula, Dreisbach 1961)
log (P/mmHg) = 7.06396 – 1024.4/(238.0 + t/°C), temp range –55 to 37°C, (Antoine eq. for liquid state,
Dreisbach 1961)
log (P/mmHg) = [–0.2185 . 6660.0/(T/K)] + 7.995166; temp range –87.7 to 162.6°C, (Antoine eq., Weast
1972–73)
172220 (20°C, Verschueren 1983)
206180 (extrapolated-Antoine eq., Boublik et al. 1984)
log (P/kPa) = 6.21132 – 962.001/(221.852 + t/°C), temp range –71.77 to 6.858°C (Antoine eq. from reported
exptl. data, Boublik et al. 1984)
202620 (Daubert & Danner 1985)
206000 (extrapolated-Antoine eq., Dean 1985, 1992)
log (P/mmHg) = 7.08212 – 960.242/(221.67 + t/°C), temp range –72 to 6°C (Antoine eq., Dean 1985, 1992)
HN
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3219
196800 (quoted lit., Riddick et al. 1986)
log (P/kPa) = 6.18886 – 1-024.40/(238.0 + t/°C), temp range not specified (Antoine eq., Riddick et al. 1986)
205300 (interpolated-Antoine eq-II., Stephenson & Malanowski 1987)
log (PL/kPa) = 6.29031 – 993.586/(–48.12 + T/K), temp range 201–280 K (Antoine eq.-I, Stephenson &
Malanowski 1987)
log (PL/kPa) = 6.20646 – 965.728/(–50.151 + T/K), temp range 277–360 K (Antoine eq.-II, Stephenson &
Malanowski 1987)
log (PL/kPa) = 7.81489 – 2369.425/(141.433 + T/K), temp range 358–438 K (Antoine eq.-III, Stephenson &
Malanowski 1987)
log (P/mmHg) = 36.9182 – 2.4965 . 103/(T/K) – 10.417·log (T/K) – 1.6287 . 10–9·(T/K) + 4.6496 . 10–6·(T/K)2;
temp range 181–438 K (vapor pressure eq., Yaws 1994)
Henry’s Law Constant (Pa·m3/mol at 25°C):
1.796 (exptl., Hine & Mookerjee 1975; quoted, Howard 1990)
1.796, 1.03 (calculated-group contribution, calculated-bond contribution, Hine & Mookerjee 1975)
2.718 (calculated-molecular structure, Russell et al. 1992)
Octanol/Water Partition Coefficient, log KOW:
–0.38 (shake flask-RC at pH 13, Wolfenden 1978)
–0.38 (Hansch & Leo 1985)
–0.38 (recommended, Sangster 1989; 1993)
–0.38 (recommended, Hansch et al. 1995)
Octanol/Air Partition Coefficient, log KOA:
2.00 (calculated-Soct and vapor pressure P, Abraham et al. 2001)
Bioconcentration Factor, log BCF:
–0.523 (calculated-KOW, Lyman et al. 1982; quoted, Howard 1990)
Sorption Partition Coefficient, log KOC:
2.638 (adsorption isotherm average for five soils, Rao & Davidson 1982; quoted, Howard 1990)
0.602; 2.212; 2.706 (Podzol soil; Alfisol soil; sediment, von Oepen et al. 1991)
2.63 (soil, calculated-MCI, Sabljic et al. 1995)
Environmental Fate Rate Constants, k, or Half-Lives, t.:
Volatilization: using Henry’s law constant, t. = 35.1 h was estimated for a model river of 1 m deep flowing at
1 m/s with a wind velocity of 3 m/s (Lyman et al. 1982; selected, Howard 1990).
Photolysis:
Oxidation: rate constant k, for gas-phase second order rate constants, kOH for reaction with OH radical, kNO3
with NO3 radical and kO3 with O3 or as indicated:
kOH = 6.54 . 10–11 cm3 molecule–1 s–1 at 299 K (Atkinson et al. 1977; quoted, Carlier et al. 1986; Atkinson
1989)
photooxidation t. = 5.9 h in air was estimated for the vapor phase reaction with hydroxyl radical of 5 . 105
radicals/cm3 in air (Atkinson et al. 1978; Atkinson 1985; quoted, Howard 1990);
kO3 = (2.61 ± 0.30) . 10–18 cm3 molecule–1 s–1 at 296 ± 2 K (Atkinson & Carter 1984; quoted, Atkinson 1985)
kOH = 6.5 . 10–11 cm3 ± molecule–1 s–1 for the gas-phase reaction with 5 . 105 OH radicals/cm3 at room temp.
having a loss rate of 2.8 d–1 (Atkinson 1985)
kOH(calc) = 63 . 10–12 cm3 molecule–1 s–1 at room temp. (Atkinson 1987).
Hydrolysis:
Biodegradation: aqueous aerobic t. = 2–79 h, based on river die-away test data (Digeronimo et al. 1979; Dojlido
1979; selected, Howard et al. 1991); aqueous anaerobic t. = 8–316 h, based on estimated unacclimated
aqueous aerobic biodegradation half-life (Howard et al. 1991).
Biotransformation:
Bioconcentration, Uptake (k1) and Elimination (k2) Rate Constants:
© 2006 by Taylor & Francis Group, LLC
3220 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
Half-Lives in the Environment:
Air: t. = 5.9 h was estimated for the vapor phase reaction with hydroxyl radical of 5 . 105 radicals/cm3 in air
(Atkinson et al. 1978; Atkinson 1985; quoted, Howard 1990);
photooxidation t. = 0.892–9.20 h, based on measured rate constant for the gas-phase reaction with OH
radical (Atkinson 1985; quoted, Howard et al. 1991) and ozone (Tuazon et al. 1978; selected, Howard
et al. 1991).
Surface water: t. = 2–79 h, based on estimated unacclimated aqueous aerobic biodegradation half-life (Howard
et al. 1991).
Groundwater: t. = 4–158 h, based on estimated unacclimated aqueous aerobic biodegradation half-life (Howard
et al. 1991).
Sediment:
Soil: t. = 86–336 h, based on soil die-away test data (Tate & Alexander 1976; Greene et al. 1981; selected,
Howard et al. 1991).
Biota:
TABLE 16.1.2.1.1
Reported vapor pressures of dimethylamine at various temperatures and the coefficients for the vapor
pressure equations
log P = A – B/(T/K) (1) ln P = A – B/(T/K) (1a)
log P = A – B/(C + t/°C) (2) ln P = A – B/(C + t/°C) (2a)
log P = A – B/(C + T/K) (3)
log P = A – B/(T/K) – C·log (T/K) (4)
log P = A – B/(T/K) – C log (T/K) + D·(T/K) – E·(T/K)2 + F·(T/K)3 (5)
Ashton et al. 1939 Stull 1947
static method summary of literature data
T/K P/Pa t/°C P/Pa
201.387 648 bp/K 280.04 –87.7 133.3
213.802 1959 mp/K 180.97 –72.2 666.6
222.078 3780 .HV/(kJ mol–1) = 26.48 (bp) –64.6 1333
232.137 7775 .Hfus/(kJ mol–1) = 5.94 (mp) –56.0 2666
242.078 14743 –46.7 5333
249.640 22949 eq. 5 P/mmHg –40.7 7999
256.449 33269 A 32.26370 –32.6 13332
262.977 46404 B 2460.10 –20.4 26664
270.182 65491 C 8.6390 –7.1 53329
275.934 84860 D 7.6055.10–3 7.4 101325
279.980 100974 E 3.51389.10–5
277.680 91519 F 5.3241.10–8 mp/°C –96.0
280.018 101141
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3221
FIGURE 16.1.2.1.1 Logarithm of vapor pressure versus reciprocal temperature for dimethylamine.
Dimethylamine: vapor pressure vs. 1/T
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0.0034 0.0038 0.0042 0.0046 0.005 0.0054 0.0058
1/(T/K)
P
( gol
S
) aP/
Aston et al. 1939
Stull 1947
b.p. = 6.88 °C m.p. = -92.18 °C
© 2006 by Taylor & Francis Group, LLC
3222 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
16.1.2.2 Trimethylamine
Common Name: Trimethylamine
Synonym: dimethylamino methane, TMA
Chemical Name: trimethylamine
CAS Registry No: 75-50-3
Molecular Formula: C3H9N, CH3N(CH3)2
Molecular Weight: 59.110
Melting Point (°C):
–117.1 (Lide 2003)
Boiling Point (C):
2.87 (Lide 2003)
Density (g/cm3 at 20°C):
0.6356 (Weast 1982–83)
Molar Volume (cm3/mol):
93 (20°C, calculated-density)
93.3 (calculated-Le Bas method at normal boiling point)
Dissociation Constant, pKa:
9.801, 9.987 (Perrin 1972; quoted, Howard 1990)
9.80 (pKa, protonated cation + 1, Dean 1985)
9.79 (pKa, Sangster 1989)
Enthalpy of Vaporization, .HV (kJ/mol):
22.85, 24.13 (25°C, bp, Dreisbach 1961)
Enthalpy of Fusion, .Hfus (kJ/mol):
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C) or as indicated:
410000 (Dean 1985)
890000 (30°C, Howard 1990)
291000 (selected, Yaws et al. 1990)
miscible (Stephenson 1993b)
Vapor Pressure (Pa at 25°C or as indicated and reported temperature dependence equations. Additional data at other
temperatures designated * are compiled at the end of this chapter):
221715* (isoteniscope, measured range 0–40°C, Swift & Hochanadel 1945)
log (P/mmHg) = 24.91300 – 2018.37/(T/K) – 6.0303 · log (T/K); temp range 0–40°C (isoteniscope method,
Swift & Hochanadel 1945)
265200* (extrapolated-regression of tabulated data, temp range –97.1 to + 2.9°C, Stull 1947)
226540 (calculated by formula, Dreisbach 1961)
log (P/mmHg) = 6.97038 – 968.7/(234.0 + t/°C), temp range –58 to 32°C (Antoine eq. for liquid state, Dreisbach 1961)
log (P/mmHg) = [–0.2185 . 6361.7/(T/K)] + 7.952370; temp range –97.1 to 2.9°C (Antoine eq., Weast 1972–73)
192500 (20°C, 30°C, Verschueren 1983)
219300, 221800 (extrapolated-Antoine eq., interpolated-Antoine eq., Boublik et al. 1984)
log (P/kPa) = 5.98554 – 1957.276/(237.664 + t/°C), temp range –80.3 to 3.45°C (Antoine eq. from reported
exptl. data, Boublik et al. 1984)
log (P/kPa) = 5.87712 – 894.366/(228.276 + t/°C), temp range 0–40°C (Antoine eq. from reported exptl. data,
Boublik et al. 1984)
214200 (Daubert & Danner 1985)
219000 (extrapolated-Antoine eq., Dean 1985, 1992)
log (P/mmHg) = 6.85755 – 955.94/(237.52 + t/°C), temp range –80 to 3°C (Antoine eq., Dean 1985, 1992)
219900 (extrapolated-Antoine eq., Stephenson & Malanowski 1987)
N
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3223
log (PL/kPa) = 6.01402 – 968.978/(–34.253 + T/K), temp range 192–277 K (Antoine eq., Stephenson &
Malanowski 1987)
log (P/mmHg) = 58.6807 – 2.686 . 103/(T/K) – 20.36·log (T/K) + 1.3131 . 10–2·(T/K) – 6.563 . 10–13·(T/K)2;
temp range 156–433 K (vapor pressure eq., Yaws 1994)
Henry’s Law Constant (Pa·m3/mol at 25°C):
6.672 (exptl., Hine & Mookerjee 1975)
12.71, 2.16 (calculated-group contribution, calculated-bond contribution, Hine & Mookerjee 1975)
15.64 (calculated-molecular structure, Russell et al. 1992)
Octanol/Water Partition Coefficient, log KOW:
0.27 (shake flask-TN, Sandell 1962; quoted, Leo et al. 1971)
0.27; 0.20 (calculated-f const., calculated-. const., Rekker 1977)
0.16 (shake flask, Hansch & Leo 1985)
0.16 (recommended, Sangster 1989)
0.16 (recommended, Hansch et al. 1995)
Octanol/Air Partition Coefficient, log KOA:
Bioconcentration Factor, log BCF:
< 0.0 (estimated-KOW, Lyman et al. 1982; quoted, Howard 1990)
Sorption Partition Coefficient, log KOC:
1.462 (soil, estimated-KOW, Lyman et al. 1982; quoted, Howard 1990)
0.602 (soil, estimated-solubility, Lyman et al. 1982; quoted, Howard 1990)
0.778; 2.365; 2.831 (Podzol soil; Alfisol soil;, sediments von Oepen et al. 1991)
Environmental Fate Rate Constants, k, or Half-Lives, t.:
Volatilization: using Henry’s law constant, t. = 11 h was estimated for a model river 1 m deep flowing at 1 m/s
with a wind velocity of 3 m/s (Lyman et al. 1982; quoted, Howard 1990).
Photolysis:
Hydrolysis:
Oxidation: rate constant k, for gas-phase second order rate constants, kOH for reaction with OH radical, kNO3
with NO3 radical and kO3 with O3 or as indicated, *data at other temperatures see reference:
kOH = 6.09 . 10–11 cm3 molecule–1 s–1 at 299 K (Atkinson et al. 1977; Atkinson 1989)
photooxidation t. = 62 d in water, based on rate constant k = 1.3 . 1010 L mol–1 s–1 for the reaction with
photochemically produced hydroxyl radicals of 1 . 10–17 mol · L–1 in water (Mill et al. 1980; Guesten
et al. 1981; quoted, Howard 1990)
kOH = 6.10 . 10–11 cm3 molecule–1 s–1 for the gas-phase reaction with 1 . 106 OH radicals/cm3 with a loss
rate of 5.0 d–1 and rate constant kO3 = 9.70 . 10–18 cm3 molecule–1 s–1 for the gas-phase reaction with
7 . 1011 O3 molecules/cm3 with a loss rate of 0.6 d–1 both at room temp. (Atkinson & Carter 1984)
calculated kOH = 64 . 10–12 cm3 molecule–1 s–1 at room temp. (SAR, Atkinson 1987).
Biodegradation:
Biotransformation:
Bioconcentration, Uptake (k1) and Elimination (k2) Rate Constants:
Half-Lives in the Environment:
Air: photooxidation t. = 4.0 h, based on rate constant k = 6.09 . 10–11 cm3 molecule–1 s–1 for the vapor-phase
reaction with photochemically produced hydroxyl radical of 8 . 105 radicals/cm3 in air at 25.5°C and
t. = 1.4 d, based on rate constant k = 9.73 . 10–18 cm3 molecule–1 s–1 for the vapor-phase reaction with ozone
of 6 . 1011 molecules/cm3 in air at 24.4°C (Atkinson 1985; GEMS 1986; quoted, Howard 1990).
Surface water: t. = 62 d, based on rate constant k = 1.3 . 1010 L mol–1 s–1 for the reaction with photochemically
produced hydroxyl radicals of 1 . 10–17 mol L–1 in water (Mill et al. 1980; Guesten et al. 1981; quoted,
Howard 1990).
© 2006 by Taylor & Francis Group, LLC
3224 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
TABLE 16.1.2.2.1
Reported vapor pressures of trimethylamine at various temperatures and the coefficients for the vapor
pressure equations
log P = A – B/(T/K) (1) ln P = A – B/(T/K) (1a)
log P = A – B/(C + t/°C) (2) ln P = A – B/(C + t/°C) (2a)
log P = A – B/(C + T/K) (3)
log P = A – B/(T/K) – C·log (T/K) (4)
Aston et al. 1944 Swift & Hochanadel 1945 Stull 1947
static method isoteniscope summary of literature data
t/°C P/Pa t/°C P/Pa t/°C P/Pa
–80.315 805 0 91059 –97.1 133.3
–74.081 1367 15 158520 –81.7 666.6
–62.339 3354 20 188651 –73.8 1333
–51.938 6777 25 221715 –65.0 2666
–46.842 9305 30 259444 –55.2 5333
–41.774 12548 35 302107 –48.8 7999
–35.617 17684 40 349437 –40.3 13332
–28.507 25624 –27.0 26664
–24.155 31772 bp/K 276.03 –12.5 53329
–23.067 33494 2.90 101325
–20.164 38401 eq. 4 P/mmHg
–15.974 46505 A 24.91300 mp/°C –117.1
–11.422 56802 B 2018.37
–8.985 63039 C 6.0303
–7.399 67346
–3.113 80208 .HV/(kJ mol–1) = 23.93
0.780 93495 at bp
2.928 101526
3.454 103611
FIGURE 16.1.2.2.1 Logarithm of vapor pressure versus reciprocal temperature for trimethylamine.
Trimethylamine: vapor pressure vs. 1/T
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0.003 0.0034 0.0038 0.0042 0.0046 0.005 0.0054 0.0058
1/(T/K)
P( gol
S
) aP
/
Aston et al. 1944
Swift & Hochanadel 1945
Stull 1947
b.p. = 2.87 °C
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3225
16.1.2.3 Ethylamine
Common Name: Ethylamine
Synonym: aminoethane, ethanamine, monoethylamine
Chemical Name: aminoethane, ethylamine
CAS Registry No: 75-04-7
Molecular Formula: C2H7N, CH3CH2NH2
Molecular Weight: 45.084
Melting Point (°C):
–80.5 (Lide 2003)
Boiling Point (°C):
16.5 (Lide 2003)
Density (g/cm3 at 20°C):
0.6829 (Dreisbach 1961; Weast 1982–83)
0.6769 (25°C, Dreisbach 1961)
Molar Volume (cm3/mol):
65.4 (5°C, Stephenson & Malanowski 1987)
66.0 (calculated-Le Bas method at normal boiling point)
Dissociation Constant, pKa:
10.79 (Perrin 1972)
10.81 (20°C, Weast 1982–83)
10.63 (protonated cation + 1, Dean 1985)
10.70 (Sangster 1989)
Enthalpy of Vaporization, .HV (kJ/mol):
27.08, 27.57 (25°C, bp, Dreisbach 1961)
Enthalpy of Fusion, .Hfus (kJ/mol):
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C):
miscible (Dean 1985; Howard 1990; Stephenson 1993b)
Vapor Pressure (Pa at 25°C or as indicated and reported temperature dependence equations. Additional data at other
temperatures designated* are compiled at the end of this section):
156200* (extrapolated-regression of tabulated data, temp range –82.3 to 16.6°C, Stull 1947)
141620 (calculated by formula, Dreisbach 1961)
log (P/mmHg) = 7.3862 – 1137.30/(235.85 + t/°C); temp range –43 to 47°C (Antoine eq. for liquid state,
Dreisbach 1961)
93325* (20°C, temp range 1.95 to 20°C, Bittrich et al. 1962)
log (P/mmHg) = [–0.2185 . 6845.1/(T/K)] + 7.973674; temp range –82.3 to 176°C, (Antoine eq., Weast
1972–73)
121570, 172220 (20°C, 30°C, Verschueren 1983)
139100 (extrapolated-Antoine eq., Boublik et al. 1984)
log (P/kPa) = 5.12561 – 559.427/(162.579 + t/°C); temp range 1.95–14.65°C (Antoine eq. from reported exptl.
data, Boublik et al. 1984)
139700 (Daubert & Danner 1985)
141000 (calculated-Antoine eq., Dean 1985, 1992)
log (P/mmHg) = 7.05413 – 987.31/(220.0 + t/°C); temp range –20 to 90°C (Antoine eq., Dean l985, 1992)
137500, 141200 (calculated-Antoine eq.-II, III, Stephenson & Malanowski 1987)
log (PL/kPa) = 6.57462 – 1167.57/(–34.18 + T/K); temp range 213–297 K (Antoine eq.-I, Stephenson &
Malanowski 1987)
log (PL/kPa) = 6.43082 – 1140.62/(–32.433 + T/K); temp range 290–449 K (Antoine eq.-II, Stephenson &
Malanowski 1987)
NH2
© 2006 by Taylor & Francis Group, LLC
3226 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
log (PL/kPa) = 6.21526 – 1009.66/(–49.804 + T/K); temp range 291–367 K (Antoine eq.-III, Stephenson &
Malanowski 1987)
log (PL/kPa) = 6.48782 – 1176.995/(–26.674 + T/K); temp range 377–456 K (Antoine eq.-IV, Stephenson &
Malanowski 1987)
140900 (calculated-Cox eq., Chao et al. 1990)
log (P/mmHg) = 33.2962 – 2.4307 . 103/(T/K) – 9.0779·log (T/K) – 1.3848 . 10–9·(T/K) + 3.8183 . 10–6·(T/K)2;
temp range 192–456 K (vapor pressure eq., Yaws 1994)
Henry’s Law Constant (Pa·m3/mol at 25°C):
1.012 (partial pressure, Butler & Ramchandani 1935)
0.683 (exptl., Hine & Mookerjee 1975)
0.859, 0.730 (calculated-group contribution, calculated-bond contribution, Hine & Mookerjee 1975)
0.421 (calculated-molecular structure, Russell et al. 1992)
Octanol/Water Partition Coefficient, log KOW:
–0.30 (shake flask-titration with ion correction, Korenman et al. 1973)
–0.16, –0.14; –0.19 (calculated-fragment const.; calculated-. const., Rekker 1977)
–0.13 (Hansch & Leo 1985)
–0.13 (recommended, Sangster 1989)
–0.14 (calculated-CLOGP, Jackel & Klein 1991)
–0.13 (recommended, Hansch et al. 1995)
Octanol/Air Partition Coefficient, log KOA:
Bioconcentration Factor, log BCF:
< 0.0 (estimated-KOW, Lyman et al. 1982; quoted, Howard 1990)
Sorption Partition Coefficient, log KOC:
Environmental Fate Rate Constants, k, or Half-Lives, t.:
Volatilization: using Henry’s law constant, t. = 2.0 d was estimated for a model river of 1 m deep flowing at
1 m/s with a wind velocity of 3 m/s (Howard 1990).
Photolysis:
Oxidation: rate constant k, for gas-phase second order rate constants, kOH for reaction with OH radical, kNO3
with NO3 radical and kO3 with O3 or as indicated, *data at other temperatures see reference:
photooxidation t. > 9.9 d for the gas-phase reaction with OH radical in air, based on the rate of disappearance
of hydrocarbon due to reaction with hydroxyl radical (Darnall et al. 1976)
kOH = 2.77 . 10–11 cm3·molecules–1·s–1 at 299 K (Atkinson et al. 1977; quoted, Carlier et al. 1986)
photooxidation t. = 321 d in water, based on a rate constant k = 2.5 . 109 L·mol–1·s–1 for the aqueous-phase
reaction with photochemically produced OH radical of 1 . 10–17 mol·L–1 (Mill et al. 1980; Guesten et al.
1981; quoted, Howard 1990)
kO3 = (2.76 ± 0.34) . 10–20 cm3·molecules–1·s–1 at 296 ± 2 K under atmospheric conditions (Atkinson & Carter
1984)
kOH = 27.7 . 10–12 cm3 molecule–1 s–1 at 299.6 K (Atkinson 1989)
Hydrolysis:
Biodegradation:
Biotransformation:
Bioconcentration, Uptake (k1) and Elimination (k2) Rate Constants:
Half-Lives in the Environment:
Air: t. > 9.9 d for the gas-phase reaction with hydroxyl radical in air, based on the rate of disappearance of
hydrocarbon due to reaction with hydroxyl radical (Darnall et al. 1976);
photooxidation t. = 8.6 h, based on rate constant k = 6.54 . 10–11 cm3·molecules–1·s–1 for the vapor-phase
reaction with an average hydroxyl radical of 5 . 105 radicals/cm3 at 25.5°C (Atkinson 1985; quoted,
Howard 1990).
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3227
Surface water: t. = 321 d, based on a rate constant k = 2.5 . 109 L·mol–1·s–1 for the aqueous-phase reaction with
photochemically produced hydroxyl radical of 1 . 10–17 mol·L–1 (Mill et al. 1980; Guesten et al. 1981;
quoted, Howard 1990).
TABLE 16.1.2.3.1
Reported vapor pressures of ethylamine at various temperatures
Stull 1947 Bittrich et al. 1962
summary of literature data
t/°C P/Pa t/°C P/Pa
–82.3 133.3 1.95 53329
–66.4 666.6 4.55 59995
–58.3 1333 6.85 66661
–48.6 2666 9.15 73327
–39.8 5333 11.05 79993
–33.4 7999 12.85 86659
–25.1 13332 14.65 93325
–12.3 26664
2.0 53329
16.6 101325
mp/°C –80.6
FIGURE 16.1.2.3.1 Logarithm of vapor pressure versus reciprocal temperature for ethylamine.
Ethylamine: vapor pressure vs. 1/T
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0.003 0.0034 0.0038 0.0042 0.0046 0.005 0.0054
1/(T/K)
P( gol
S
) aP/
Bittrich et al. 1962
Stull 1947
b.p. = 16.5 °C m.p. = -80.5 °C
© 2006 by Taylor & Francis Group, LLC
3228 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
16.1.2.4 Diethylamine
Common Name: Diethylamine
Synonym: aminoethylethane, N-ethylethanamine
Chemical Name: aminoethylethane, diethylamine
CAS Registry No: 109-89-7
Molecular Formula: C4H11N, CH3CH2NHCH2CH3
Molecular Weight: 73.137
Melting Point (°C):
–49.8 (Lide 2003)
Boiling Point (°C):
55.5 (Lide 2003)
Density (g/cm3 at 20°C):
0.6993, 0.6926 (20°C, 25°C, Dreisbach. 1961)
0.7056 (Weast 1982–83)
0.7070, 0.7016 (20°C, 25°C, Riddick et al. 1986)
Molar Volume (cm3/mol):
103.4 (20°C, calculated-density)
109.0 (exptl. at normal bp, Lee et al. 1972)
111.9 (calculated-Le Bas method at normal boiling point,)
Dissociation Constant, pKa:
10.98 (Perrin 1965; quoted, Howard 1990)
10.80 (35°C, Perrin 1972)
10.80 (protonated cation + 1, Dean 1985)
11.07 (Sangster 1989)
Enthalpy of Vaporization, .HV (kJ/mol):
31.38, 29.50 (25°C, bp, Dreisbach 1961)
31.32, 29.07 (25°C, bp, Riddick et al. 1986)
Enthalpy of Fusion, .Hfus (kJ/mol):
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C or as indicated):
815000 (14°C, quoted, Verschueren 1983)
miscible (Dean 1985; Riddick et al. 1986; Yaws et al. 1990)
miscible (Stephenson 1993b)
Vapor Pressure (Pa at 25°C and or as indicated reported temperature dependence equations. Additional data at other
temperatures designated* are compiled at the end of this section):
26664* (21°C, summary of literature data, temp range –33.0 to 55.5°C, Stull 1947)
31130 (calculated by formula, Dreisbach 1961)
log (P/mmHg) = 7.14099 – 1209.9/(229.0 + t/°C); temp range –15 to 90°C (Antoine eq. for liquid state, Dreisbach
1961)
39997* (31.45°C, temp range 31.45–60.58°C, Bittrich & Kauer 1962)
31471* (25.17°C, temp range 19.73–40.22°C, Kilian & Bittrich 1965)
log (P/mmHg) = [–0.2185 . 7307.5/(T/K)] + 7.701718; temp range –33.0 to 210°C (Antoine eq., Weast 1972–73)
26660, 38660 (20°C, 30°C, Verschueren 1983)
30110, 31310 (extrapolated-Antoine eq., interpolated-Antoine eq., Boublik et al. 1984)
log (P/kPa) = 4.97981 – 580.448/(143.68 + t/°C); temp range 31.45–60.58°C (Antoine eq. from reported exptl.
data, Boublik et al. 1984)
log (P/kPa) = 5.84728 – 994.478/(203.53 + t/°C); temp range 19.758–40.22°C (Antoine eq. from reported exptl.
data, Boublik et al. 1984)
NH
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3229
31130 (selected, Riddick et al. 1986)
log (P/kPa) = 4.92649 – 583.297/(144.145 + t/°C); temp range not specified (Antoine eq., Riddick et al. 1986)
31490 (extrapolated-Antoine eq., Stephenson & Malanowski 1987)
log (PL/kPa) = 5.96802 – 1058.538/(–61.331 + T/K); temp range 302–328 K (Antoine eq.-I, Stephenson &
Malanowski 1987)
log (PL/kPa) = 5.92678 – 1028.405/(–66.2061 + T/K); temp range 325–437 K (Antoine eq.-II, Stephenson &
Malanowski 1987)
log (P/mmHg) = 5.8016 – 583.3/(144.1 + t/°C); temp range 31–61°C (Antoine eq., Dean 1992)
log (P/mmHg) = 32.626 – 2.4918 . 103/(T/K) – 9.3285·log (T/K) + 3.990 . 10–3·(T/K) + 1.1732 . 10–12·(T/K)2;
temp range 223–497 K (vapor pressure eq., Yaws 1994)
Henry’s Law Constant (Pa·m3/mol at 25°C):
2.596 (exptl., Hine & Mookerjee 1975)
2.537, 2.37 (calculated-group contribution, calculated-bond contribution, Hine & Mookerjee 1975)
6.67 (calculated-vapor liquid equilibrium VLE data, Yaws et al. 1991)
Octanol/Water Partition Coefficient, log KOW:
0.43 (shake flask, Collander 1951)
0.57 (shake flask-titration, Sandell 1962)
0.60, 0.61; 0.70 (calculated-fragment const.; calculated-. const., Rekker 1977)
0.58 (Hansch & Leo 1985)
0.58 (20°C, shake flask-GC, Takayama et al. 1985)
0.81 (HPLC-k. correlation, Eadsforth 1986)
0.58 (recommended, Sangster 1989)
0.58 (recommended, Hansch et al. 1995)
Octanol/Air Partition Coefficient, log KOA:
Bioconcentration Factor, log BCF:
0.210 (calculated-KOW, Lyman et al. 1982; quoted, Howard 1990)
Sorption Partition Coefficient, log KOC:
1.699 (soil, calculated-KOW, Lyman et al. 1982; quoted, Howard 1990)
Environmental Fate Rate Constants, k, or Half-Lives, t.:
Volatilization: using Henry’s law constant, t. ~ 31.6 h for a model river 1 m deep flowing at 1 m/s with a wind
velocity of 3 m/s (estimated, Lyman et al. 1982; quoted, Howard 1990).
Photolysis:
Oxidation: photooxidation t. > 9.9 d for the gas-phase reaction with hydroxyl radical in air, based on the rate
of disappearance of hydrocarbon due to reaction with OH radical (Darnall et al. 1976);
photooxidation t. = 0.21 d in air, based on an estimated second-order rate constant k = 77.1 . 10–12 cm3
molecule–1 s–1 for the vapor-phase reaction with photochemically produced hydroxyl radicals of 5 . 105
radicals/cm3 in air (Atkinson 1987; quoted, Howard 1990).
Hydrolysis:
Biodegradation:
Biotransformation:
Bioconcentration, Uptake (k1) and Elimination (k2) Rate Constants:
Half-Lives in the Environment:
Air: t. > 9.9 d for the gas-phase reaction with hydroxyl radicals in air, based on the rate of disappearance of
hydrocarbon due to reaction with hydroxyl radical (Darnall et al. 1976);
t. = 0.21 d, based on an estimated rate constant k ~ 77.1 . 10–12 cm3 molecule–1 s–1 for the vapor-phase
reaction with photochemically produced hydroxyl radicals of 5 . 105 radicals/cm3 in air (Atkinson 1987;
quoted, Howard 1990).
© 2006 by Taylor & Francis Group, LLC
3230 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
TABLE 16.1.2.4.1
Reported vapor pressures of diethylamine at various temperatures
Stull 1947 Bittrich & Kauer 1962 Kilian & Bittrich 1965
summary of literature data
t/°C P/Pa t/°C P/Pa t/°C P/Pa
–33.0 1333 31.45 39997 19.73 24718
–22.6 2666 34.75 46663 25.17 31471
–11.3 5333 38.05 53329 30.31 39343
–4.0 7999 41.1 59995 34.99 47596
6.0 13332 43.85 66661 40.22 58582
21.0 26664 46.5 73327
38.0 53329 48.85 79993
55.5 101325 51.10 86659
53.20 93325
mp/°C –38.9 55.53 101325
57.05 106658
59.00 113324
60.58 119990
FIGURE 16.1.2.4.1 Logarithm of vapor pressure versus reciprocal temperature for diethylamine.
Diethylamine: vapor pressure vs. 1/T
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0.0028 0.0032 0.0036 0.004 0.0044 0.0048
1/(T/K)
P( gol
S
) aP
/
Bittrich & Kauer 1962
Kilian & Bittrich 1965
Stull 1947
b.p. = 55.5 °C m.p. = -49.8 °C
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3231
16.1.2.5 n-Propylamine
Common Name: Propylamine
Synonym: 1-aminopropane, 1-propanamine, n-propylamine
Chemical Name: aminopropane, n-propylamine
CAS Registry No: 107-10-8
Molecular Formula: C3H9N, CH3CH2CH2NH2
Molecular Weight: 59.110
Melting Point (°C):
–84.75 (Lide 2003)
Boiling Point (°C):
47.22 (Lide 2003)
Density (g/cm3 at 20°C):
0.7173 (Dreisbach 1961; Weast 1982–83; Dean 1985; Riddick et al. 1986)
0.7123 (25°C, Dreisbach 1961)
Molar Volume (cm3/mol):
82.4 (liquid molar volume, Kamlet et al. 1986, 1987)
88.2 (calculated-Le Bas method at normal boiling point)
Dissociation Constant, pK:
10.74, 10.789 (20°C, Perrin 1972)
10.71 (pKa, 20°C, Weast 1982–83)
10.57 (pKBH
+ , Dean 1985; Riddick et al. 1986)
10.68 (pKa, Sangster 1989)
Enthalpy of Vaporization, .HV (kJ/mol):
31.13, 29.73 (25°C, bp, Dreisbach 1961)
31.26, 29.54 (25°C, bp, Riddick et al. 1986)
Enthalpy of Fusion, .Hfus (kJ/mol):
10.974 (Riddick et al. 1986)
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C):
miscible (Dean 1985; Stephenson 1993b)
miscible (Riddick et al. 1986; Howard 1990; Yaws et al. 1990)
Vapor Pressure (Pa at 25°C and reported temperature dependence equations. Additional data at other temperatures
designated * are compiled at the end of this section):
41800* (interpolated-regression of tabulated data, temp range –64.4 to 48.5°C, Stull 1947)
41050 (calculated by formula, Dreisbach 1961)
log (P/mmHg) = 7.2672 – 1218.1/(229.9 + t/°C); temp range –20 to 81°C (Antoine eq. for liquid state, Dreisbach
1961)
42100* (ebulliometry, calculated-Antoine eq., Osborn & Douslin 1968)
log (P/mmHg) = 6.92646 – 1044.028/(t/°C + 210.833); temp range 23–77.6°C (ebulliometric method, Antoine
eq., Osborn & Douslin 1968)
log [(P/atm) = [1 – 320.379 ± (T/K)] . 10^{0.922208 – 10.51259 . 10–4·(T/K) + 11.25530 . 10–7·(T/K)2}, temp
range: 34–77.6°C (ebulliometric method, Cox eq., Osborn & Douslin 1968)
log (P/mmHg) = [–0.2185 . 7408.0/(T/K)] + 7.867998; temp range –64.4 to 214.5°C (Antoine eq., Weast
1972–73)
32660 (20°C, 31°C, Verschueren 1983)
38550; 42110 (22.97°C, quoted exptl., calculated-Antoine eq., Boublik et al. 1984)
log (P/kPa) = 6.05146 – 1044.082/(210.84 + t/°C); temp range 22.97–77.6°C (Antoine eq. from reported exptl.
data of Osborn & Douslin 1968, Boublik et al. 1984)
42120 (calculated-Antoine eq., Dean 1985, 1992)
NH2
© 2006 by Taylor & Francis Group, LLC
3232 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
log (P/mmHg) = 6.92651 – 1044.05/(210.84 + t/°C); temp range: 23–77°C (Antoine eq., Dean l985, 1992)
41050 (Riddick et al. 1986)
log (P/kPa) = 6.05136 – 1044.028/(210.833 + t/°C); temp range not specified (Antoine eq., Riddick et al. 1986)
42120 (interpolated-Antoine eq., Stephenson & Malanowski 1987)
log (PL/kPa) = 6.04693 – 1041.725/(–62.596 + T/K); temp range 295–351 K (Antoine eq., Stephenson &
Malanowski 1987)
42125 (calculated-Cox eq., Chao et al. 1990)
log (P/mmHg) = 24.6420 – 2.3152 . 103/(T/K) – 5.8711·log (T/K) – 4.6258 . 10–11·(T/K) + 1.582 . 10–6·(T/K)2;
temp range 190–497 (vapor pressure eq., Yaws 1994)
Henry’s Law Constant (Pa m3/mol at 25°C):
1.274 (partial pressure, Butler & Ramchandani 1935)
0.784; 0.732 (exptl.; calculated-group contribution, Hine & Mookerjee 1975)
1.330 (calculated-bond contribution, Hine & Mookerjee 1975)
0.637 (calculated-molecular structure, Russell et al. 1992)
2.01 (gas stripping-GC, Altschuh et al. 1999)
Octanol/Water Partition Coefficient, log KOW:
0.28 (shake flask-GC, Korenman et al. 1973)
0.37, 0.39; 0.31‘ (calculated-f const.; calculated-. const., Rekker 1977)
0.48 (shake flask-GC, pH 13, Yakayama et al. 1985)
0.48 (recommended, Sangster 1989)
0.48 (recommended, Hansch et al. 1995)
Octanol/Air Partition Coefficient, log KOA:
Bioconcentration Factor, log BCF:
–0.886 (estimated-KOW, Lyman et al. 1982; quoted, Howard 1990)
Sorption Partition Coefficient, log KOC:
< 1.699 (soil, estimated-KOW, Lyman et al. 1982; quoted, Howard 1990)
Environmental Fate Rate Constants, k, or Half-Lives, t.:
Volatilization: using Henry’s law constant, t. ~ 2.44 d was estimated for a model river 1 m deep flowing at
1 m/s with a wind speed of 3 m/s (estimated, Lyman et al. 1982; quoted, Howard 1990).
Photolysis:
Oxidation: photooxidation t. = 12 h in air, based on estimated rate constant k = 3.21 . 10–12 cm3·molecule–1·s–1
for the vapor-phase reaction with hydroxyl radical of 5 . 105/cm3 at 25°C in the atmosphere (Atkinson 1987;
quoted, Howard 1990).
Hydrolysis:
Biodegradation:
Biotransformation:
Bioconcentration, Uptake (k1) and Elimination (k2) Rate Constants:
Half-Lives in the Environment:
Air: t. = 12 h, based on estimated second-order rate constant of 3.21 . 10–12 cm3·molecule–1·s–1 for the vaporphase
reaction with hydroxyl radical of 5 . 105/cm3 at 25°C in the atmosphere (Atkinson 1987; quoted,
Howard 1990).
© 2006 by Taylor & Francis Group, LLC
Nitrogen and Sulfur Compounds 3233
TABLE 16.1.2.5.1
Reported vapor pressures of n-propylamine at various temperatures
Stull 1947 Osborn & Douslin 1968
summary of literature data ebulliometric method
t/°C P/Pa t/°C P/Pa
–64.4 133.3 22.973 38547
–46.3 666.6 27.750 47359
–37.2 1333 32.564 57803
–27.1 2666 37.414 70109
–16.0 5333 42.304 84525
–9.0 7999 47.229 101325
0.50 13332 52.193 120798
15.0 26664 57.195 143268
31.5 53329 62.235 169052
48.5 101325 67.314 198530
72.430 232087
mp/°C –83.0 77.587 270110
FIGURE 16.1.2.5.1 Logarithm of vapor pressure versus reciprocal temperature for n-propylamine.
n -Propylamine: vapor pressure vs. 1/T
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0.0026 0.003 0.0034 0.0038 0.0042 0.0046 0.005 0.0054
1/(T/K)
log(PS/Pa)
Osborn & Douslin 1968
Stull 1947
b.p. = 47.22 °C m.p. = -84.75 °C
© 2006 by Taylor & Francis Group, LLC
3234 Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals
16.1.2.6 n-Butylamine
Common Name: Butylamine
Synonym: 1-aminobutane, n-butylamine. 1-butanamine
Chemical Name: 1-aminobutane, n-butylamine
CAS Registry No: 109-73-9
Molecular Formula: C4H11N, CH3CH2CH2CH2NH2
Molecular Weight: 73.137
Melting Point (°C):
–49.1 (Dreisbach 1961; Riddick et al. 1986; Stephenson & Malanowski 1987; Lide 2003)
Boiling Point (°C):
77.0 (Lide 2003)
Density (g/cm3 at 20°C):
0.7414 (Dreisbach 1961; Weast 1982–83)
0.7392 (Riddick et al. 1986)
Molar Volume (cm3/mol):
98.8 (20°C, calculated-density)
110.4 (calculated-Le Bas method at normal boiling point)
Dissociation Constant, pK:
10.77 (Perrin 1965; pKa, 20°C, Weast 1982–83; Howard 1990)
10.65 (Perrin 1972)
10.64 (pKa, protonated + 1, Dean 1985; Sangster 1989)
10.77 (pKBH + , Riddick et al. 1986)
Enthalpy of Vaporization, .HV (kJ/mol):
35.54, 32.11 (25°C, bp, Dreisbach 1961)
35.74, 31.80 (25°C, bp, Riddick et al. 1986)
Enthalpy of Fusion, .Hfus (kJ/mol):
Entropy of Fusion, .Sfus (J/mol K):
Fugacity Ratio at 25°C (assuming .Sfus = 56 J/mol K), F: 1.0
Water Solubility (g/m3 or mg/L at 25°C):
miscible (Dean 1985; Howard 1990; Yaws et al. 1990)
miscible (Riddick et al. 1986)
miscible (Stephenson 1993b)
Vapor Pressure |
