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Atmospheric Multiphase Chemistry
Atmospheric Multiphase Chemistry
Fundamentals of Secondary Aerosol Formation
Hajime Akimoto
National Institute for Environmental Studies
Tsukuba, Japan
Jun Hirokawa
Hokkaido University
Sapporo, Japan
This edition first published 2020
© 2020 John Wiley & Sons Ltd
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Library of Congress Cataloging-in-Publication Data

Names: Akimoto, Hajime, author. | Hirokawa, Jun, author.
Title: Atmospheric multiphase chemistry : fundamentals of secondary aerosol
formation / Hajime Akimoto, Jun Hirokawa.
Description: First edition. | Hoboken, NJ : Wiley-Blackwell, 2020. |
Includes bibliographical references and index.
Identifiers: LCCN 2019051976 (print) | LCCN 2019051977 (ebook) | ISBN
9781119422426 (hardback) | ISBN 9781119422396 (adobe pdf ) | ISBN
9781119422402 (epub)
Subjects: LCSH: Atmospheric aerosols. | Chemical reactions. | Multiphase
flow.
Classification: LCC QC882.42 .A45 2020 (print) | LCC QC882.42 (ebook) |
DDC 551.51/13–dc23
LC record available at https://lccn.loc.gov/2019051976
LC ebook record available at https://lccn.loc.gov/2019051977
Cover Design: Wiley

Cover Image: © Daniel Haug/Getty Images
Set in 10/12pt WarnockPro by SPi Global, Chennai, India
Printed and bound by CPI Group (UK) Ltd, Croydon, CR0 4YY
10 9 8 7 6 5 4 3 2 1
v
Contents
Preface xiii
1 Historical Background of Atmospheric Secondary Aerosol Research 1

1.1 Introduction 1
1.2 Secondary Inorganic Aerosols 1
1.2.1 Sulfate 2
1.2.2 Nitrate 3
1.3 Secondary Organic Aerosols 4
1.3.1 Photochemical Smog 5
1.3.2 Blue Haze 6
References 7
2 Fundamentals of Multiphase Chemical Reactions 13

2.1 Introduction 13
2.2 Gas–Liquid Phase Equilibrium and Equilibrium in Liquid Phase 13
2.2.1 Fundamentals of Thermodynamics 14
2.2.1.1 Internal Energy and Enthalpy 14
2.2.1.2 Entropy 16
2.2.1.3 Gibbs Energy 18
2.2.1.4 Chemical Potential 19
2.2.2 Chemical Equilibrium and Equilibrium Constant 21
2.2.2.1 Chemical Equilibrium 21
2.2.2.2 Equilibrium Constant of Gas-Phase Reaction 22
2.2.2.3 Equilibrium Constant of Liquid-Phase Reaction 24
2.2.2.4 Temperature Dependence of Equilibrium Constant 26
2.2.3 Gas–Liquid Equilibrium and Henry’s Law Constant 29
2.2.4 Hydration of Carbonyl Compounds and Effective Henry’s Law
Constant 31
2.2.5 pH and Equilibrium in the Aqueous Solution 32
2.2.5.1 Dissociation Equilibrium of Pure Water and pH 32
2.2.5.2 Ion Dissociation and Equilibrium in Aqueous Solution 33
2.3 Reactions in the Liquid Phase 35
2.3.1 Thermodynamics and Activity Coefficients of Nonideal Solutions 35
vi Contents
2.3.1.1 Salting-in, Salting-out 38

2.3.2 Chemical Kinetics of Aqueous-Phase Reaction 39
2.3.2.1 Diffusion Process and Chemical Reaction Kinetics 39
2.3.2.2 Transition State Theory of Solution Reaction and
Thermodynamic Expression 42
2.3.3 Cage Effect and Aqueous-Phase Solvent Effect 46
2.3.3.1 Cage Effect 46
2.3.3.2 Solvent Effect in the Aqueous Phase 48
2.4 Uptake Coefficient and Resistance Model 51
2.4.1 Accommodation Coefficient and Uptake Coefficient 52
2.4.2 Resistance Model 54
2.5 Physical Chemistry of Interface Reaction 56
2.5.1 Langmuir-Hinshelwood Mechanism and Eley-Rideal Mechanism 56
2.5.2 Resistance Model Including Interface Reaction 59
2.5.3 Surface Tension of Air–Water Interface and Thermodynamics of
Accommodation Coefficient 65
2.5.3.1 Surface Tension 65
2.5.3.2 Thermodynamics of Accommodation Coefficient at
Air–Water Interface 68
2.6 Chemical Compositions and Physical Characters of Particles 71
2.6.1 Elemental and Molecular Composition of Particles 72
2.6.1.1 Inorganic Elements and Compounds 72
2.6.1.2 Organic Compounds 74
2.6.1.3 van Krevelen Diagram 77
2.6.2 Molecular Composition and Vapor Pressure 78
2.6.3 Gas-Particle Partitioning and Volatility Basis Set Model 84
2.6.3.1 Gas-Particle Partitioning and SOA Formation Yield 84
2.6.3.2 Volatility Basis Set Model 88
2.6.3.3 Gas-Aqueous Phase Partitioning of Hydrophilic
Compounds 90
2.6.4 Phase State of Particles and Mass Transfer 93
References 95
3 Gas-Phase Reactions Related to Secondary Organic Aerosols 107

3.1 Introduction 107
3.2 Ozone Reactions 107
3.2.1 Properties and Reactions of Criegee Intermediates 108
3.2.1.1 Direct Detection of Criegee Intermediate and Molecular
Structure 110
3.2.1.2 Formation of CH2 OO in Ozone-Ethene Reaction 115
3.2.1.3 Formation of syn- and anti-CH3 CHOO in Ozone-Alkene
Reactions 118
3.2.2 Alkenes and Dialkenes 130
3.2.2.1 Ethene 130
3.2.2.2 >C3 Alkenes 132
3.2.2.3 1,3-Butadiene 134
3.2.3 Isoprene 135
Contents vii
3.2.4 Cycloalkenes 139

3.2.4.1 Cyclohexene 139
3.2.4.2 1-Methylcyclohexene 141
3.2.4.3 Methylenecyclohexane 144
3.2.5 Monoterpenes 144
3.2.5.1 α-Pinene 145
3.2.5.2 β-Pinene 148
3.2.5.3 Limonene 150
3.2.6 Sesquiterpenes 155
3.3 OH Radical-Induced Oxidation Reactions 160
3.3.1 Alkanes 160
3.3.1.1 Reactions of Alkyl Peroxy Radicals 165
3.3.1.2 Reactions of Alkoxy Radicals 165
3.3.2 Alkynes 170
3.3.3 Alkenes, Dialkenes, and Cycloalkenes 171
3.3.3.1 Alkenes 171
3.3.3.2 1,3-Butadiene 173
3.3.3.3 Cycloalkenes and Methylene cyclohexane 174
3.3.4 Isoprene 175
3.3.4.1 Fundamental Processes of OH-Induced Oxidation
Reaction 175
3.3.4.2 HOx Radicals Regeneration Reaction 178
3.3.4.3 Formation of Isoprene Hydroxy Hydroperoxide (ISOPOOH)
and Isoprene Epoxydiol (IEPOX) 179
3.3.4.4 Formation of Hydroxy Isoprene Nitrates 180
3.3.4.5 Reactions of Methyl Vinyl Ketone and Methacrolein 182
3.3.5.1 α-Pinene 183
3.3.5.2 β-Pinene 185
3.3.6 Monocyclic Aromatic Hydrocarbons 189
3.3.6.1 Benzene 189
3.3.6.2 Toluene 192
3.3.7 Polycyclic Aromatic Hydrocarbons 195
3.3.7.1 Naphthalene 196
3.3.7.2 Other Polycyclic Aromatic Hydrocarbons 198
3.3.8 Carbonyl Compounds: OH Radical Reactions and Photolysis 199
3.3.8.1 Glyoxal 199
3.3.8.2 Methylglyoxal 202
3.3.8.3 Glycolaldehyde 204
3.3.8.4 Hydroxyacetone 207
3.4 NO3 Oxidation Reactions 209
3.4.1 Isoprene 209
3.4.2.1 α-Pinene 213
3.4.2.2 β-Pinene 214
viii Contents
3.4.3 Monocyclic and Polycyclic Aromatic Hydrocarbons 217

3.4.3.1 Phenol, and Cresol 217
3.4.3.2 Naphthalene 218
3.4.3.3 Other Polycyclic Aromatic Hydrocarbons 219
References 219
4 Aqueous-Phase Reactions Related to Secondary Organic Aerosols 245

4.2 OH Radical Reactions 246
4.2.1 UV Absorption Spectrum of OH Radicals in Aqueous Solution 246
4.2.2 Formation of OH Radicals in Cloud/Fog Droplets and Deliquescent
Aerosols 248
4.2.3 Reaction Rate Constants of OH Radicals in the Aqueous Phase 254
4.2.4 Reactions of Formaldehyde and OH Radical Chain Reaction 257
4.2.5 OH Radical Reactions and Photolysis of ≥C2 Carbonyl
Compounds 262
4.2.5.1 Glyoxal and Glyoxylic Acid 262
4.2.5.2 Methylglyoxal, Pyruvic Acid, and Acetic Acid 264
4.2.5.3 Glycolaldehyde and Glycolic Acid 267
4.2.5.4 Methacrolein and Methyl Vinyl Ketone 268
4.2.6 Oligomer Formation Reactions from ≥C2 Carbonyl Compounds 270
4.2.6.1 Glyoxal and Methylglyoxal 272
4.2.6.2 Methyl Vinyl Ketone and Methacrolein 273
4.3 Nonradical Reactions 275
4.3.1 Diels-Alder Reaction 276
4.3.2 Hemiacetal and Acetal Formation Reactions 277
4.3.2.1 Glyoxal 279
4.3.2.3 1,4-Hydroxycarbonyl Compounds 281
4.3.3 Aldol Reaction 281
4.3.3.1 Acetaldehyde 282
4.3.3.3 Methyl Vinyl Ketone and Methacrolein 284
4.3.4 Esterification Reactions 285
4.4 Formation Reactions of Organic Sulfates 287
4.4.1 C2 and C3 Carbonyl Compounds 287
4.4.3 Isoprene 291
4.4.4 Monocyclic and Polycyclic Aromatic Hydrocarbons 291
4.5 Formation Reactions of Organic Nitrogen Compounds 292
4.5.1 Organic Nitrates 292
4.5.2 Imidazoles 293
References 295
5 Heterogeneous Oxidation Reactions at Organic Aerosol Surfaces 309

5.2 Aging of Organic Aerosols in the Atmosphere 309
Contents ix
5.3 Reactions of Ozone 313

5.3.1 Oleic Acid and Unsaturated Long-Chain Carboxylic Acids 314
5.3.2 Squalene 316
5.4 Reactions of OH Radicals 320
5.4.1 Squalane and Long-Chain Alkanes 320
5.4.2 Levoglucosan, Erythritol, and Hopane 325
5.4.3 Saturated Dicarboxylic Acids 326
5.4.4 Squalene and Long-Chain Unsaturated Carboxylic Acids 328
5.5 Reactions of NO3 Radicals 332
5.5.1 Levoglucosan, Squalane, Long-Chain Alkane, and Alkanoic Acid 332
5.5.2 Squalene and Oleic Acid 334
References 336
6 Reactions at the Air–Water and Air–Solid Particle Interface 343

6.2 Molecular Pictures and Reactions at the Air–Water Interface 344
6.2.1 Thermodynamics of Adsorption 345
6.2.1.1 OH, HO2 , and O3 346
6.2.1.2 Organic and Inorganic Compounds 348
6.2.2 Microscopic Picture of Molecules 349
6.2.2.1 Air–Pure Water Interface 350
6.2.2.2 Hydrophilic Organic Compounds 352
6.2.2.3 Amphiphilic Organic Compounds (Surfactants) 356
6.2.2.4 Hydrophobic Organic Compounds 357
6.2.2.5 NH3 and SO2 358
6.2.3 Reactions of O3 and Organic Compounds 359
6.2.3.1 Oleic Acid 360
6.2.3.2 Sesquiterpene Criegee Intermediates 360
6.2.3.3 Polycyclic Aromatic Hydrocarbons 361
6.2.4 Reactions of OH Radicals and Organic Compounds 362
6.2.4.1 Carboxylic and Dicarboxylic Acids 362
6.2.4.2 Organic Sulfur Compounds 364
6.3 Air–Sea Salt Particle, Seawater, and Sulfate/Nitrate Aerosol Interface 365
6.3.1 Microscopic View of Interface of Air and Alkaline Halide Aqueous
Solution 366
6.3.2 Reactions at the Interface of Sea Salt and Alkali Halide Aqueous
Solution 368
6.3.2.1 Reaction with O3 369
6.3.2.2 Reaction with OH Radicals 371
6.3.2.3 Uptake of HO2 Radicals 372
6.3.2.4 Reaction with N2 O5 372
6.3.2.5 Reaction with HNO3 373
6.3.3 Reactions of Organic Compounds at the Air–Seawater and Air–Sea
Salt Interface 375
x Contents
6.3.4 Microscopic View of the Interface of Air and Sulfate/Nitrate Aqueous

Solution 377
6.3.4.1 Sulfate Ion (SO4 2− ) 377
6.3.4.2 Nitrate Ion (NO3 − ) 378
6.4 Reactions on Snow/Ice Surface 379
6.4.1 Formation of NOy in the Photochemical Reaction of NO3 − 379
6.4.2 Formation of Inorganic Halogens on the Snow Ice and Sea Ice
Surface 382
6.4.2.1 Reaction with O3 382
6.4.2.2 Reaction with OH Radicals 383
6.4.2.3 Reactions with N2 O5 384
6.5 Interface of Water and Mineral Dust, Quartz, and Metal Oxide Surface 385
6.5.1 Microscopic View of Adsorbed Water on Mineral Surface 386
6.5.2 HONO Formation Reaction from NO2 on the Mineral Surface 390
6.5.2.1 Dark Reaction 390
6.5.2.2 Photochemical Reaction 392
6.5.3 Reaction of Organic Monolayer on Mineral Surface 394
References 396
7 Atmospheric New Particle Formation and Cloud Condensation Nuclei 415

7.2 Classical Homogeneous Nucleation Theory 415
7.2.1 Homogeneous Nucleation in One-Component Systems 415
7.2.2 Homogeneous Nucleation in Two-Component Systems 419
7.3 Atmospheric New Particle Formation 422
7.3.1 New Particle Formation Rate and Growth Rate 422
7.3.2 Sulfuric Acid in New Particle Formation 425
7.3.3 Basic Substances in New Particle Formation 427
7.3.4 Organic Species in New Particle Formation 430
7.3.5 Other Species in New Particle Formation 433
7.3.5.1 Iodine Oxides 433
7.3.5.2 Atmospheric Ions 434
7.3.6 Field Observation of Nanoclusters 435
7.4 Aerosol Hygroscopicity and Cloud Condensation Nuclei 436
7.4.1 Köhler Theory 436
7.4.2 Nonideality of Solution in a Droplet 441
7.4.3 Hygroscopicity Parameter, 𝜅 442
References 446
8 Field Observations of Secondary Organic Aerosols453

8.2 Global Budget of Aerosols 453
8.3 Analysis Methods of Ambient Aerosol Compositions 458
8.3.1 Positive Matrix Factorization 458
8.3.2 Mass Spectrum Peak Intensity and Elemental Ratio 459
8.3.3 Elemental Composition 460
8.4 Marine Air 461
Contents xi
8.5 Forest Air 465

8.5.1 Amazon Tropical Forest 465
8.5.2 Finland Boreal Forest 469
8.6 Urban/Rural Air 472
8.6.1 Characterization of Ambient Aerosols 472
8.6.1.1 PMF Analysis 472
8.6.1.2 Mass Signal Intensity Ratio and Elemental Ratio 474
8.6.1.3 Particle Size Distribution 477
8.6.1.4 Elemental Composition 478
8.6.2 Molecular Composition 479
8.6.2.1 Dicarboxylic Acid 480
8.6.2.2 Plant Origin VOC Tracers 481
8.6.2.3 Anthropogenic VOC Tracer 484
8.6.2.4 Organic Sulfate 485
8.6.2.5 Organic Nitrates and Imidazoles 486
8.6.2.6 High-Molecular-Weight Compounds and Oligomers 489
References 493
Index 509
xiii
Preface
Reaction kinetics and mechanism are a significant part of the fundamentals of atmo-
spheric chemistry. The chemical reaction system in the atmosphere is composed of
homogeneous reactions in the gas and liquid phases and heterogeneous processes
involving particle surfaces. Among them, the study of gas-phase homogeneous reaction
system in the atmosphere has evolved since the Chapman theory in the 1930s to
explain the stratospheric ozone layer, and developed dramatically after 1970s with
photochemical air pollution as a trigger. It is now almost established and summarized
in many bibliographies, including a book by one of present authors (H.A.) discussed in
Chapter 3.
In contrast, although the heterogeneous reaction system in the atmosphere has
developed substantially with acid rain and stratospheric ozone hole as turning points,
the studies have long been confined mainly to inorganic species. The research field of
aerosols and heterogeneous kinetics has undergone dramatic changes since the 2000s,
when the importance of secondary organic aerosols as cloud condensation nuclei was
pointed out. Also, secondary organic aerosols have been recognized as important as
inorganic sulfate and nitrate as a constituent of PM2.5 , which is concerned from the
point of human health.
The formation mechanism of secondary organic aerosols involves condensation
of reaction products of homogeneous gas-phase reactions, uptake of the gas-phase
products onto the particle surface, complex formation and reaction at the interface,
homogeneous aqueous-phase reaction, and evaporation from a particle to the gas
phase. We call series of these processes multiphase reaction chemistry.
This book intends to serve as a reference book on fundamentals of atmospheric mul-
tiphase chemistry. Gas- and aqueous-phase reactions, heterogeneous oxidation pro-
cesses, and air–water interface and solid particle surface reactions related to secondary
organic aerosol formation are first described. After that, new particle formation, cloud
condensation nucleus activity, and field observation of organic aerosols are discussed.
The book can serve as a comprehensive reference for graduate students and profession-
als who are interested in homogeneous and heterogeneous atmospheric reactions of
organic species related to aerosols.
xiv Preface
The field of atmospheric multiphase chemistry is still a rapidly developing research

area. Many studies described in this book have not become fully established, and future
revisions are likely.
Finally, we would like to acknowledge Drs. Michihiro Mochida, Satoshi Inomata,
Kei Sato, Yasuhiro Sadanaga, and Shinichi Enami, who read the manuscript in their
respective parts and gave us valuable comments.
October, 2019 Hajime Akimoto

Jun Hirokawa
1
Historical Background of Atmospheric Secondary Aerosol

Research
1.1 Introduction
Trace components in the tropospheric atmosphere consist of gaseous molecules and
particulate matters. Most of gaseous molecules in the atmosphere do not have absorp-
tion bands in the visible region. Some species such as ozone and nitrogen dioxide have
the absorption, but they are invisible to the naked eye under the normal atmospheric
conditions because their absorbance are small. In contrast, since the particulate mat-
ters intercept sunlight and small particles scatter strongly the solar radiation, they are
captured easily by the naked eye as haze. Thus, particulate matters in the atmosphere
called atmospheric aerosols have been studied from relatively early days in relation to
air pollution historically.
These atmospheric aerosols are divided broadly into the primary species released
directly from emission sources and the secondary compounds formed by chemical
reactions in the atmosphere. Further, secondary particulate matter can be classified
into secondary inorganic aerosol and secondary organic aerosol (SOA).
This book aims at the understanding of chemical reactions forming secondary aerosols
in the gas phase, in the liquid phase, and at their interface, particularly focusing on
organic aerosols. Therefore, most of the descriptions are focused on organic species, and
inorganic species are addressed whenever necessary. As for the formation of secondary
inorganic aerosols, detailed discussion has been given by the textbook of Seinfeld and
Pandis (2016).
In this chapter, historical background of research on atmospheric secondary aerosols,
including inorganic aerosols, is described looking back before 1980s, when the atmo-
spheric chemistry was founded as one of the academic fields of the global environmental
sciences.
1.2 Secondary Inorganic Aerosols

The first capture of atmospheric secondary inorganic aerosol such as nitrate and
sulphate was in the form of precipitation component, and their historical reviews are
available by Eriksson (1952a, 1952b) and Möller (2008). First discovery of nitrate in
precipitation was made by Marggraf (1751), a German chemist, and mineral species
(silica and lime), sea salt component (sodium and chloride), ammonium, and organics
as brown residue were also detected together with nitrate. It was the earlier half of
Atmospheric Multiphase Chemistry: Fundamentals of Secondary Aerosol Formation,
First Edition. Hajime Akimoto and Jun Hirokawa.
© 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.
2 1 Historical Background of Atmospheric Secondary Aerosol Research
nineteenth century when Liebig (1835) advocated a theory that atmospheric nitrogen
compounds deposited on ground are essential to plant growth as nutrient salt absorbed
by roots, leading to a revolution of agricultural chemistry. Thus, atmospheric nitrate,
the main component of the plant nutrient, had been discovered from long ago as a
precipitation constituent (Miller 1905; Eriksson 1952a; Möller 2008). On the other
hand, the discovery of sulphate was delayed nearly 100 years after that of nitrate. From
the view point of air pollution in Manchester, UK, Smith (1852) described based on
the analysis of precipitation that three kinds of air can be found: (i) with carbonate of
ammonia in the remote field; (ii) with sulphate of ammonia in the suburbs; and (iii) with
sulfuric acid in the urban area (Cowling 1982). The described ammonium carbonate
((NH4 )2 CO3 ), ammonium sulfate ((NH4 )2 SO4 ), and sulfuric acid (H2 SO4 ) are formed
secondarily by the chemical reactions in the gas phase or in the fog water from atmo-
spheric trace gaseous species, CO2 , NH3 , and SO2 . These aerosols are water-soluble,
and recognized as major components of “acid rain” after taken into precipitation.
Incidentally, the term of acid rain was used for the first time in the monograph of Smith
(1872) as accredited by Cowling (1982). Since then, the measurement of nitrate and
ammonium had been made in many places in Europe in the latter half of nineteenth
century from the interest of agricultural chemistry, while sulfate had been measured in
the eastern part of United States since the 1910s (Cowling 1982).
Hydrogen ion concentration (pH) has been measured since the 1950s, started in
Europe and United States, over a wide area. Owing to these wide-area observations,
spatial distribution and temporal trends of pH and chemical components of precip-
itation became to be known well in Europe (Emanuelsson et al. 1954; Barrett and
Brodin 1955; Odén 1976) and North America (Junge and Werby 1958; Gorham and
Gordon 1960; Cogbill 1976). The acid rain causing acidification of lakes and rivers
and their impact on fishery was then brought up as a social problem internationally.
The quantitative research on the formation of sulfate and nitrate as secondary inorganic
aerosol had been developed rapidly as “acid rain” became social concern.
1.2.1 Sulfate
In the earlier studies on acid rain, it was thought that sulfur dioxide (SO2 ), primary air
pollutants whose atmospheric concentration had increased rapidly after the Industrial
Revolution, was taken up into fog water droplets and converted to sulfate by oxidation
in the aqueous phase (Junge and Ryan 1958; Junge 1963):
H2 O O2 NH4 +
SO2 −−−−→ SO3 2− −−−−n+−→ SO4 2− −−−−−→ (NH4 )2 SO4 (1.1)
M
The rate limiting stage of this process is the oxidation step of SO3 2− to SO4 2− , and the
oxidation by O2 had been studied for a long time (Fudakowski 1873; Backstrom 1934).
However, the oxidation rate of SO3 2− by O2 was found to be very slow (Fuller and Crist
1941; Brimblecombe and Spedding 1974). Therefore, this reaction is not important for
O2 alone as the oxidation reaction of SO2 in the atmosphere, but it was found that the
reaction is accelerated by the coexistence of trace metal ions such as Fe3+ , Cu2+ , and
Mn2+ (Reinders and Vles 1925; Junge and Ryan 1958; Brimblecombe and Spedding 1974;
Hegg and Hobbs 1978). The effects of transition metal ions on the SO2 oxidation in the
aqueous phase still leaves a lot of unknowns, and the studies are ongoing (Deguillaume
et al. 2005; Harris et al. 2013; Herrmann et al. 2015).
1.2 Secondary Inorganic Aerosols 3
In 1970s, the importance of the reaction of O3 and H2 O2 , formed secondarily in the

photochemically polluted atmosphere, was pointed out. The pioneering studies were
made by Penkett and Garland (1974), Erickson et al. (1977), and Larson et al. (1978)
for O3 , and by Mader (1958), Hoffmann and Edwards (1975), and Penkett et al. (1979)
for H2 O2 . Later studies on these aqueous phase reactions revealed that the oxidation
by H2 O2 is more important at lower pH than 7, and those of O3 become important in
the higher pH region. Details of these aqueous-phase reactions are summarized in the
textbooks by Akimoto (2016, pp. 363–372), and Seinfeld and Pandis (2016).
Atmospheric oxidation reactions of SO2 to SO4 2− were studied earlier for the
aqueous-phase reactions, and the gas-phase reactions was noted later by Cox and
Penkett (1972). The years of 1970s are the era that OH radical chain reactions were
proposed and demonstrated to cause photochemical air pollution (Akimoto 2016,
pp. 288–290). The importance of the reaction of SO2 and OH for the oxidation of SO2
was deduced based on the measured rate constant of the reaction (Eggleton and Cox
1978; Davis et al. 1979). Later, Stockwell and Calvert (1983) showed the oxidation
process of SO2 with OH as
OH + SO2 + M → HOSO2 + M (1.2)
HOSO2 + O2 → HO2 + SO3 (1.3)
SO3 + H2 O + M → H2 SO4 + M (1.4)
HO2 + NO → NO2 + OH (1.5)
This implies that the HOSO2 forms H2 SO4 without terminating the OH chain reaction.
The SO2 oxidation mechanism in the gas-phase has thus been established. Although
the relative importance of gas- and aqueous-phase reactions varies widely, depending
on meteorological conditions. It is thought in general that both processes are important
(Barrie et al. 2001). Most of sulfate in particles exist as ammonium sulfate ((NH4 )2 SO4 )
or ammonium bisulfate (NH4 HSO4 ), and a part of them exists as sulfuric acid (H2 SO4 )
when NH3 is in short stoichiometrically as observed in the sub-micron particles in many
urban samples (van den Heuvel and Mason 1963; Ludwig and Robinson 1965; Wagman,
Lee, and Axt 1967).
1.2.2 Nitrate
The measurement of nitrate (NO3 − ) in precipitation has been reported in United
States early in 1920s from the interest in agricultural chemistry (Wilson 1926). Its
atmospheric concentrations increased rapidly, accompanying with the rapid increase
of fossil fuel combustion. It has been monitored since the 1950s as an important
secondary inorganic aerosol next to SO4 2− (Junge 1954; Lee and Patterson 1969). For
example, the equivalent-basis fractions of SO4 2− and NO3 − in precipitation in Eastern
United States in early 1960s are reported as ca. 60% and ca. 20%, respectively (Likens
and Bormann 1974). Particularly, large amounts of nitrates were reported, together
with sulfate and organic aerosols existing in photochemical smog mentioned in the
next section (Renzetti and Doyle 1959; Lundgren 1970; Appel et al. 1978).
Since the rate constant of the reaction:
OH + NO2 + M → HNO3 + M, (1.6)
is one order of magnitude larger than the reaction, OH + SO2 + M, under the atmo-
spheric conditions, and the Henry’s law constant of NO2 is two orders of magnitude
smaller than SO2 (Table 2.2), nitric acid (HNO3 ) in the atmosphere is thought to be
formed in the gas phase and then taken into the aqueous phase (Orel and Seinfeld 1977).
Meanwhile, a formation pathway other than (1.6) is considered to be the hydrolysis of
N2 O5 formed via NO3 by the reaction of O3 and NO2 (Orel and Seinfeld 1977):
NO2 + O3 → NO3 + O2 (1.7)
NO2 + NO3 + M → N2 O5 + M (1.8)
N2 O5 + H2 O → 2 HNO3 (1.9)
The rate constant of Reaction (1.9) in the gas phase as a homogeneous reaction is
very small, <2.0 × 10−21 cm3 molecule−1 s−1 (Burkholder et al. 2015), and the heteroge-
neous reaction on the particle surface is thought to be more important (Mozurkewich
and Calvert 1988). The NO3 radical involved in this reaction process has absorption
bands in the visible region and photolysed easily by sunlight, so that the formation of
HNO3 by this heterogeneous reaction process is thought to be important in the night-
time (Richards 1983; Heikes and Thompson 1983).
The gaseous nitric acid, ammonia, and ammonium nitrate formed from them are
thought to be in equilibrium:
NH3 (g) + HNO3 (g) ⇆ NH4 NO3 (s), (1.10)
and comparison between model estimate based on the thermodynamic parameters
(Stelson et al. 1979) and field observation for the formation of nitrate have been made
(Harrison and Pio 1983; Hildemann et al. 1984). Reaction (1.10) is reversible reaction,
and the particulate NH4 NO3 increases with the decrease of temperature, and thus the
concentration ratio of nitrate is known to increase in winter and at dawn. Multiphase
models that treat sulfuric and nitric acid simultaneously have been developed in 1980s
(Bassett and Seinfeld 1983; Saxena et al. 1983).
Gaseous HNO3 reacts with sea salt (NaCl) on the surface to give sodium nitrate by
releasing HCl:
NaCl(s) + HNO3 (g) → NaNO3 (s) + HCl(g). (1.11)
Although it has been presumed that the reaction causes the decrease of chlorine to
sodium ratio in the sea salt in the vicinity of continents and brings the nitrate in coarse
particles (Robbins et al. 1959), the reaction has been validated by laboratory experiments
only after the latter half of 1990s (De Haan and Finlayson-Pitts 1997; Wahner et al. 1998).
Thus, nitrates have the characteristics that they exist as NH4 NO3 in submicron parti-
cles in the inland and as NaNO3 in coarse particles (2–8 μm) in the coastal urban area
(Lee and Patterson 1969; Cronn et al. 1977).
1.3 Secondary Organic Aerosols

Existence of organic materials in the precipitation was noted by Marggraf (1751) in the
middle of eighteenth century, and they were more clearly identified as humic acid-like
substances in the first half of the nineteenth century (Lampadius 1837; Möller 2008).
1.3 Secondary Organic Aerosols 5
However, the trigger to wide concern on the particulate organic compounds was the
discovery of carcinogenic polyaromatic hydrocarbons (PAHs) in the diesel exhaust and
urban atmosphere in the middle of twentieth century (e.g. Waller 1952; Kotin et al. 1954;
Stocks and Campbell 1955; Wynder and Hoffmann 1965). Further findings of many oxy-
genated compounds in the atmospheric aerosols were made in the photochemical smog.
1.3.1 Photochemical Smog

In the middle of the 1940s, new type of smog totally different from conventional air pol-
lution due to SO2 , sulfate, and coal fly ash, spread in Los Angeles basin, and became
a social problem by causing visibility reduction, eye and throat irritation, and particu-
larly big damage to agriculture (Middleton et al. 1950; Finlayson-Pitts and Pitts 2000).
Although the cause of so-named Los Angeles smog was unexplained at the beginning,
Haagen-Smit (1952), and Haagen-Smit, Bradley and Fox (1956) elucidated for the first
time that it is ascribed to the toxic substances, including ozone and other strongly oxidiz-
ing compounds so-named photochemical oxidants, formed by the solar irradiation to the
mixtures of nitrogen oxides and non-methane hydrocarbons (NMHCs) emitted from
automobile exhaust. Such atmospheric photochemical processes were systematized by
Leighton (1961), and his book, Photochemistry of Air Pollution is now a classic of atmo-
spheric photochemistry. Los Angeles smog was later called photochemical smog (e.g.
Rogers 1958), and the term, photochemical air pollution, is now widely used including
more general concept (e.g. Robinson 1972).
In photochemical smog, other than gaseous oxidants, many kinds of organic aerosols
together with sulfate and nitrate were found as particulate matter, and these were shown
to be SOAs, formed by the photo-irradiation of the mixtures of NOx and NMHCs such
as auto exhaust (Mader et al. 1952; Renzetti and Doyle 1959). Incidentally, the NMHC
was used as a general term for the collectives of short-lived hydrocarbons, excluding
methane, which has a longer atmospheric lifetime of nearly 10 years and does not
contribute to urban photochemical air pollution directly. Recently, instead of NMHC,
the term nonmethane volatile organic compounds (NMVOC) has been more widely
used to include oxygen-containing organic compounds other than hydrocarbons. From
the early days of the study on the formation mechanism of photochemical smog, there
was interest in what kinds of hydrocarbons generate SOAs more effectively. Studies of
Haagen-Smit (1952) showed that cyclic hydrocarbons with double bonds such as cyclo-
hexene, indene, and cyclopentadiene easily form low-volatile oxygenated compounds
with higher yields of aerosols, since the multiple functional groups are introduced by
the ring-opening reactions. This was later confirmed by O’Brien, Holmes, and Bokian
(1975), and they reported α-pinene having a cyclic double bond and dialkenes such as
isoprene form aerosols with the higher yields, and monocyclic aromatic hydrocarbons
such as xylenes also form aerosols with the lower yields.
In the organic aerosols, particulate alkanes, alkenes, alkylbenzenes, naphthalene,
etc. were detected as primary organic aerosols (POAs) released directly from emission
sources, and pinonic acid, adipic acid, phenols, alkyl nitrates, etc. as SOA formed in
the atmosphere. Primary aerosols are not correlated with ozone, but the secondary
aerosols have a high correlation with ozone and have peak concentration in early
afternoon. Such clear distinction between the POA and SOA was made in the middle
of 1970s (Appel, Colodny, and Wesolowski 1976; Cronn et al. 1977). These early studies
showed that alcohols, carboxylic acids, and carbonyl compounds are included in the
aerosols by use of infrared absorption spectroscopy and mass spectrometry (Cukor
et al. 1972; Ciaccio et al. 1974; Cronn et al. 1977). Also, it was revealed that atmospheric
carbonaceous aerosol sampled in California consisted of elemental carbon (EC) and
organic carbon (OC) (Appel, Colodny and Wesolowski 1976).
1.3.2 Blue Haze

It is experienced for a long time that the atmosphere in the boundary layer over forests is
covered by blue haze after the air is cleaned by rain in summer. In 1950s, a botanist, Went
(1960a) addressed the interest to this phenomenon from the viewpoint of atmospheric
aerosols. In the “Blue Mountains” near Sydney, Australia, and “Blue Ridges” near the
Smoky Mountains in Tennessee, United States, such blue haze are often visible (Ferman,
Wolff, and Kelly 1981). Went (1960a) mentioned that a similar phenomenon in Tuscany,
Italy, was described in a note by Leonardo da Vinci a long time ago in sixteenth century.
This kind of haze is not natural dust or mist, nor the effects of biomass burning or air
pollution, and can be seen in dry air irrelevant to water vapor. From these considerations
Went (1960a) concluded that blue haze is due to the Tyndall effect described by Tyndall
(1869) in the middle of nineteenth century, a phenomenon that a light path can be seen
bright from an oblique due to scatter of light by fine particles in air. He proposed that
when the fine particles with a diameter of the order of 0.1 μm exist in the atmosphere,
blue light in the solar light is effectively scattered and blue haze is visible.
As for the possibility of formation of such sub-micron fine particles over the clean
forests, Went (1960b) suggested that the photochemical smog reaction of hydrocarbons
such as terpenes and isoprene emitted by plants. However, atmospheric concentrations
of such biogenic hydrocarbons were not known in early 1960s. They were measured for
the first time by Rasmussen and Went (1965), and total concentration of isoprene and
terpenes up to ∼10 ppbv was reported in several forest highlands in United States.
Later measurement of chemical composition of field aerosols at Great Smoky
Mountains showed that the main component of fine particles is sulfate and the fraction
of organic compounds are relatively small (Stevens et al. 1980; Ferman, Wolff, and
Kelly 1981) in those days. Seasonality of the aerosol components were shown that
concentrations of sulfate and organic aerosols are high in summer and that of nitrate
is high in winter, reflecting the photochemical formation of SO4 2− and OA, and
temperature-dependent gas-solid equilibrium of NH4 NO3 (Day, Malm, and Kreiden-
weis 1997). Meanwhile, although the measurement of chemical analysis of aerosols in
Blue Mountains in Australia is scarce, solvent extracted organics contains n-alkane,
n-alkanoic acid, and n-alcohol, which compose lipids contained in plant wax (Simoneit
et al. 1991).
It is interesting to note that the prototype of SOA formation from biogenic and anthro-
pogenic hydrocarbons was thus shown in early studies more than 50 years ago. The
research on SOA has been developed extensively after the year of 2000 being related
to the interests in the impact on human health of PM2.5 and in the climate impact of
aerosols.
References 7
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13
Fundamentals of Multiphase Chemical Reactions
2.1 Introduction
Chemical reaction systems in the atmosphere are composed of homogeneous reactions
in the gas phase, homogeneous liquid-phase reactions in deliquescent aerosol particles
and water droplets, and heterogeneous reactions at the particle surface. Among them,
physicochemical fundamentals of photochemistry and kinetics in the homogenous gas
phase reactions have already been well established in principle, and detailed explana-
tion has been given in a previous book by one of the present authors (Akimoto 2016)
and many textbooks introduced therein. In contrast, many aspects of atmospheric mul-
tiphase chemical reactions, including uptake of chemical species from gas phase to par-
ticle surface, heterogeneous reactions at the surface, and homogeneous aqueous phase
reactions, have not yet been well established. In this chapter, fundamentals of physi-
cal chemistry relevant to the formation and transformation of atmospheric aerosols are
described. The values of physical constants appearing in this book and the conversion
factors of energy units between kJ, kcal, and eV are given in Tables 2.1 and 2.2.
In this chapter, fundamentals of optical properties, such as scattering of light and
photoabsorption by atmospheric fine particles, and the photochemistry related to the
photolysis at the surface of fine particles are not covered. The former topics are covered
by the textbook by Mishchenko et al. (2002) and Kokhanovsky (2008), but the system-
atic research on the latter topic has not been developed well and is still open to future
research.
2.2 Gas–Liquid Phase Equilibrium and Equilibrium in Liquid

Phase
In the gas–liquid phase equilibrium, the experimental discovery that the amount of
gaseous molecules dissolving into the liquid phase is proportional to the partial pressure
of the substance in the gas phase was made by a British chemist, William Henry (1803),
and the proportional constant is called Henry’s law constant after his name. The Henry’s
law constant is an important parameter in atmospheric chemistry, which describes the
partitioning of trace chemical species between the air and the cloud/fog and aqueous
aerosol particles. Before the specific discussion of Henry’s law constant and ion disso-
ciation, general treatment of thermodynamics of chemical equilibrium is described in
this section as underlying bases.
Atmospheric Multiphase Chemistry: Fundamentals of Secondary Aerosol Formation,
First Edition. Hajime Akimoto and Jun Hirokawa.
© 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.
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The Project Gutenberg eBook of Iamblichus
on the mysteries of the Egyptians, Chaldeans,
and Assyrians
This ebook is for the use of anyone anywhere in the United
States and most other parts of the world at no cost and with
almost no restrictions whatsoever. You may copy it, give it away
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are not located in the United States, you will have to check the
laws of the country where you are located before using this
eBook.
Title: Iamblichus on the mysteries of the Egyptians, Chaldeans,

and Assyrians
Author: Iamblichus
Contributor: Porphyry
Translator: Thomas Taylor
Release date: January 29, 2024 [eBook #72815]
Language: English
Original publication: London: Bertram Dobell & Reeves and

Turner, 1895
Credits: Richard Tonsing, MFR, and the Online Distributed

Proofreading Team at https://www.pgdp.net (This file
was produced from images generously made available
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*** START OF THE PROJECT GUTENBERG EBOOK IAMBLICHUS

ON THE MYSTERIES OF THE EGYPTIANS, CHALDEANS, AND
ASSYRIANS ***
Transcriber’s Note:
New original cover art included with this eBook is
granted to the public domain.
IAMBLICHUS
ON
The Mysteries
OF THE
EGYPTIANS, CHALDEANS, AND
ASSYRIANS.
TRANSLATED FROM THE GREEK
BY
THOMAS TAYLOR.
Ο δε Αριστοτελης προς Αντιπατρον περι Αλεξανδρου γραφων, εφη μη

μονον εκεινῳ προσηκειν οτι πολλων κρατει μεγαφρονειν, αλλ’ ουδεν
ηττον ει τις ορθως γινωσκει περι θεων.
Plutarch.
Second Edition.
LONDON:
BERTRAM DOBELL,
77 CHARING CROSS ROAD, W.C.
AND
REEVES AND TURNER,
5 WELLINGTON STREET, STRAND.
MDCCCXCV.
ADVERTISEMENT.
The various translations and original works of Thomas Taylor,

though still in request by the more zealous students of ancient
philosophy and occult science, have now become so scarce and
expensive that it is only within the power of comparatively wealthy
collectors to obtain them. This is a matter for regret, inasmuch as it
cannot be affirmed that his writings have been, or are likely to be
superseded, or that they are without value. They can hardly be
neglected without loss by those who desire to understand the
systems of philosophy which satisfied the spiritual needs of the
antique world. It is not possible, even for the most fervent believer in
modern “progress,” to dismiss the speculations of the ancient
philosophers as antiquated notions which have had their day and no
longer possess interest or value. The names of Socrates, Plato, and
Aristotle can never grow dim with age, nor is it possible to conceive a
time when men shall cease to study and reverence them. As the
disciple, the translator, and the expounder of these and of other
sages of antiquity, Thomas Taylor deserves to be held in honour and
remembrance, and it would be a misfortune if his labours remained
unknown because of the scarcity of his books. It is for this reason
that the present reprint has been undertaken; and it is hoped that it
will meet with such a measure of success as may encourage the
republication of various other works by the same author. It has been
printed in handsome style and published at a moderate price in
order that it may be regarded as a desirable addition to the scholar’s
library, while yet it will not tax severely the means of the not too
wealthy student. For the rest it is only necessary to say that this
reprint is, in size, number of pages, type, and general get-up, an
almost exact facsimile of the original edition, which was first printed
in 1821. No alterations or additions have been made in or to the
original text, as it is thought that those who care for Taylor’s writings
will prefer to have them in their integrity. Should it be found
possible, however, to continue the series it is intended to prefix to a
future volume an essay on Taylor, which will contain a biography of
him, and a critical estimate of his writings.
May, 1895.
INTRODUCTION.
It appears to me that there are two descriptions of persons by

whom the present work must be considered to be of inestimable
worth, the lovers of antiquity and the lovers of ancient philosophy
and religion. To the former of these it must be invaluable, because it
is replete with information derived from the wise men of the
Chaldeans, the prophets of the Egyptians, the dogmas of the
Assyrians, and the ancient pillars of Hermes; and to the latter,
because of the doctrines contained in it, some of which originated
from the Hermaic pillars, were known by Pythagoras and Plato, and
were the sources of their philosophy; and others are profoundly
theological, and unfold the mysteries of ancient religion with an
admirable conciseness of diction, and an inimitable vigour and
elegance of conception. To which also may be added, as the colophon
of excellence, that it is the most copious, the clearest, and the most
satisfactory defence extant of genuine ancient theology.
This theology, the sacred operations pertaining to which called
theurgy are here developed, has for the most part, since the
destruction of it, been surveyed only in its corruptions among
barbarous nations, or during the decline and fall of the Roman
empire, with which, overwhelmed with pollution, it gradually fell,
and at length totally vanished from what is called the polished part of
the globe. This will be evident to the intelligent reader from the
following remarks, which are an epitome of what has been elsewhere
more largely discussed by me on this subject, and which also
demonstrate the religion of the Chaldeans, Egyptians, and Greeks to
be no less scientific than sublime.
In the first place, this theology celebrates the immense principle of
things as something superior even to being itself; as exempt from the
whole of things, of which it is nevertheless ineffably the source; and
does not, therefore, think fit to enumerate it with any triad[1] or order
of beings. Indeed it even apologizes for giving the appellation of the
most simple of our conceptions to that which is beyond all
knowledge and all conception. It denominates this principle
however, the one and the good; by the former of these names
indicating its transcendent simplicity, and by the latter its
subsistence as the object of desire to all beings. For all things desire
good. At the same time, however, it asserts that these appellations
are in reality nothing more than the parturitions of the soul, which,
standing as it were in the vestibules of the adytum of deity, announce
nothing pertaining to the ineffable, but only indicate her
spontaneous tendencies towards it, and belong rather to the
immediate offspring of the first God than to the first itself. Hence, as
the result of this most venerable conception of the supreme, when it
ventures not only to denominate it, though ineffable, but also to
assert something of its relation to other things, it considers this as
preeminently its peculiarity, that it is the principle of principles; it
being necessary that the characteristic property of principle, after the
same manner as other things, should not begin from multitude, but
should be collected into one monad as a summit, and which is the
principle of all principles.
The scientific reasoning from which this dogma is deduced is the
following. As the principle of all things is the one, it is necessary that
the progression of beings should be continued, and that no vacuum
should intervene either in incorporeal or corporeal natures. It is also
necessary that every thing which has a natural progression should
proceed through similitude. In consequence of this, it is likewise
necessary that every producing principle should generate a number
of the same order with itself, viz. nature, a natural number; soul, one
that is psychical (i. e. belonging to soul); and intellect an intellectual
number. For if whatever possesses a power of generating, generates
similars prior to dissimilars, every cause must deliver its own form
and characteristic peculiarity to its progeny; and before it generates
that which gives subsistence to progressions, far distant and separate
from its nature, it must constitute things proximate to itself
according to essence, and conjoined with it through similitude. It is,
therefore, necessary from these premises, since there is one unity,
the principle of the universe, that this unity should produce from
itself, prior to every thing else, a multitude of natures characterized
by unity, and a number the most of all things allied to its cause; and
these natures are no other than the Gods.
According to this theology, therefore, from the immense principle
of principles, in which all things causally subsist, absorbed in
superessential light, and involved in unfathomable depths, a
beauteous progeny of principles proceed, all largely partaking of the
ineffable, all stamped with the occult characters of deity, all
possessing an overflowing fulness of good. From these dazzling
summits, these ineffable blossoms, these divine propagations, being,
life, intellect, soul, nature, and body depend; monads suspended
from unities, deified natures proceeding from deities. Each of these
monads, too, is the leader of a series which extends from itself to the
last of things, and which, while it proceeds from, at the same time
abides in, and returns to, its leader. And all these principles, and all
their progeny, are finally centred and rooted by their summits in the
first great all-comprehending one. Thus all beings proceed from, and
are comprehended in, the first being: all intellects emanate from one
first intellect; all souls from one first soul; all natures blossom from
one first nature; and all bodies proceed from the vital and luminous
body of the world. And, lastly, all these great monads are
comprehended in the first one, from which both they and all their
depending series are unfolded into light. Hence this first one is truly
the unity of unities, the monad of monads, the principle of
principles, the God of Gods, one and all things, and yet one prior to
all.
No objections of any weight, no arguments but such as are
sophistical, can be urged against this most sublime theory, which is
so congenial to the unperverted conceptions of the human mind, that
it can only be treated with ridicule and contempt in degraded,
barren, and barbarous ages. Ignorance and impious fraud, however,
have hitherto conspired to defame those inestimable works[2] in
which this and many other grand and important dogmas can alone
be found; and the theology of the ancients has been attacked with all
the insane fury of ecclesiastical zeal, and all the imbecile flashes of
mistaken wit, by men whose conceptions on the subject, like those of
a man between sleeping and waking, have been turbid and wild,
phantastic and confused, preposterous and vain.
Indeed, that after the great incomprehensible cause of all, a divine
multitude subsists, cooperating with this cause in the production and
government of the universe, has always been, and is still, admitted by
all nations and all religions, however much they may differ in their
opinions respecting the nature of the subordinate deities, and the
veneration which is to be paid to them by man; and however
barbarous the conceptions of some nations on this subject may be,
when compared with those of others. Hence, says the elegant
Maximus Tyrius, “You will see one according law and assertion in all
the earth, that there is one God, the king and father of all things, and
many Gods, sons of God, ruling together with him. This the Greek
says, and the Barbarian says, the inhabitant of the continent, and he
who dwells near the sea, the wise and the unwise. And if you proceed
as far as to the utmost shores of the ocean, there also there are Gods,
rising very near to some, and setting very near to others.”[3]
The deification, however, of dead men, and the worshiping men as
Gods, formed no part of this theology, when it is considered
according to its genuine purity. Numerous instances of the truth of
this might be adduced, but I shall mention for this purpose, as
unexceptionable witnesses, the writings of Plato, the Golden
Pythagoric Verses,[4] and the Treatise of Plutarch on Isis and Osiris.
All the works of Plato, indeed, evince the truth of this position, but
this is particularly manifest from his Laws. The Golden verses order
that the immortal Gods be honoured first, as they are disposed by
law; afterwards the illustrious Heroes, under which appellation the
author of the verses comprehends also angels and dæmons, properly
so called; and in the last place, the terrestrial dæmons, i. e. such good
men as transcend in virtue the rest of mankind. But to honour the
Gods as they are disposed by law, is, as Hierocles observes, to
reverence them as they are arranged by their demiurgus and father;
and this is to honour them as beings not only superior to man, but
also to dæmons and angels. Hence, to honour men, however
excellent they may be, as Gods, is not to honour the Gods according
to the rank in which they are placed by their Creator; for it is
confounding the divine with the human nature, and is thus acting
directly contrary to the Pythagoric precept. Plutarch too, in his above
mentioned treatise, most forcibly and clearly shows the impiety of
worshiping men as Gods.[5]
“So great an apprehension indeed,” says Dr. Stillingfleet,[6] “had
the Heathens of the necessity of appropriate acts of divine worship,
that some of them have chosen to die, rather than to give them to
what they did not believe to be God. We have a remarkable story to
this purpose in Arrian and Curtius[7] concerning Callisthenes.
Alexander arriving at that degree of vanity as to desire to have divine
worship given him, and the matter being started out of design among
the courtiers, either by Anaxarchus, as Arrian, or Cleo the Sicilian, as
Curtius says; and the way of doing it proposed, viz. by incense and
prostration; Callisthenes vehemently opposed it, as that which
would confound the difference of human and divine worship, which
had been preserved inviolable among them. The worship of the
Gods had been kept up in temples, with altars, and images, and
sacrifices, and hymns, and prostrations, and such like; but it is by no
means fitting, says he, for us to confound these things, either by
lifting up men to the honours of the Gods, or depressing the Gods to
the honours of men. For if Alexander would not suffer any man to
usurp his royal dignity by the votes of men; how much more justly
may the Gods disdain for any man to take their honours to himself.
And it appears by Plutarch,[8] that the Greeks thought it a mean and
base thing for any of them, when sent on any embassy to the kings of
Persia, to prostrate themselves before them, because this was only
allowed among them in divine adoration. Therefore, says he, when
Pelopidas and Ismenias were sent to Artaxerxes, Pelopidas did
nothing unworthy, but Ismenias let fall his ring to the ground, and
stooping for that, was thought to make his adoration; which was
altogether as good a shift as the Jesuits advising the crucifix to be
held in the mandarin’s hands while they made their adorations in the
Heathen temples in China.
Conon[9] also refused to make his adoration, as a disgrace to his
city; and Isocrates[10] accuses the Persians for doing it, because
herein they showed that they despised the Gods rather than men, by
prostituting their honours to their princes. Herodotus mentions
Sperchies and Bulis, who could not with the greatest violence be
brought to give adoration to Xerxes, became it was against the law
of their country to give divine honour to men.[11] And Valerius
Maximus[12] says, “the Athenians put Timagoras to death for doing
it; so strong an apprehension had possessed them, that the manner
of worship which they used to their Gods, should be preserved sacred
and inviolable.” The philosopher Sallust also, in his Treatise on the
Gods and the World, says, “It is not unreasonable to suppose that
impiety is a species of punishment, and that those who have had a
knowledge of the Gods, and yet despised them, will in another life be
deprived of this knowledge. And it is requisite to make the
punishment of those who have honoured their kings as Gods to
consist in being expelled from the Gods.”[13]
When the ineffable transcendency of the first God, which was
considered as the grand principle in the Heathen religion by the best
theologists of all nations, and particularly by its most illustrious
promulgators, Orpheus, Pythagoras, and Plato, was forgotten, this
oblivion was doubtless the principal cause of dead men being deified
by the Pagans. Had they properly directed their attention to this
transcendency they would have perceived it to be so immense as to
surpass eternity, infinity, self-subsistence, and even essence itself,
and that these in reality belong to those venerable natures which are,
as it were, first unfolded into light from the unfathomable depths of
that truly mystic unknown, about which all knowledge is refunded
into ignorance. For, as Simplicius justly observes, “It is requisite that
he who ascends to the principle of things should investigate whether
it is possible there can be any thing better than the supposed
principle; and if something more excellent is found, the same inquiry
should again be made respecting that, till we arrive at the highest
conceptions, than which we have no longer any more venerable. Nor
should we stop in our ascent till we find this to be the case. For there
is no occasion to fear that our progression will be through an
unsubstantial void, by conceiving something about the first
principles which is greater and more transcendent than their nature.
For it is not possible for our conceptions to take such a mighty leap
as to equal, and much less to pass beyond, the dignity of the first
principles of things.” He adds, “This, therefore, is one and the best
extension [of the soul] to [the highest] God, and is, as much as
possible, irreprehensible; viz. to know firmly, that by ascribing to
him the most venerable excellences we can conceive, and the most
holy and primary names and things, we ascribe nothing to him which
is suitable to his dignity. It is sufficient, however, to procure our
pardon [for the attempt], that we can attribute to him nothing
superior.”[14] If it is not possible, therefore, to form any ideas equal to
the dignity of the immediate progeny of the ineffable, i. e. of the first
principles of things, how much less can our conceptions reach that
thrice unknown darkness, in the reverential language of the
Egyptians,[15] which is even beyond these? Had the Heathens,
therefore, considered as they ought this transcendency of the
supreme God, they would never have presumed to equalize the
human with the divine nature, and consequently would never have
worshiped men as Gods. Their theology, however, is not to be
accused as the cause of this impiety, but their forgetfulness of the
sublimest of its dogmas, and the confusion with which this oblivion
was necessarily attended.
But to return to the present work. To some who are conversant
with the writings of Porphyry, who know how high he ranks among
the best of the Platonists, and that he was denominated by them, on
account of his excellence, the philosopher, it may seem strange that
he should have been so unskilled in theological mysteries, and so
ignorant of the characteristics of the beings superior to man, as by
his epistle to Anebo he may appear to have been. That he was not,
however, in reality thus unskilful and ignorant, is evident from his
admirable Treatise on Abstinence from Animal Food, and his
Αφορμαι προς τα νοητα, or Auxiliaries to Intelligibles. His apparent
ignorance, therefore, must have been assumed for the purpose of
obtaining a more perfect and copious solution of the doubts
proposed in his Epistle, than he would otherwise have received. But
at the same time that this is admitted, it must also be observed, that
he was inferior to Iamblichus in theological science, who so greatly
excelled in knowledge of this kind, that he was not surpassed by any
one, and was equaled by few. Hence he was denominated by all
succeeding Platonists the divine, in the same manner as Plato, “to
whom,” as the acute Emperor Julian remarks, “he was posterior in
time only, but not in genius.”[16]
The difficulties attending the translation of this work into English
are necessarily great, not only from its sublimity and novelty, but
also from the defects of the original. I have, however, endeavoured to
make the translation as faithful and complete as possible; and have
occasionally availed myself of the annotations of Gale, not being able
to do so continually, because for the most part, where philosophy is
concerned, he shows himself to be an inaccurate, impertinent, and
garrulous smatterer.
THE
EPISTLE OF PORPHYRY
TO THE
EGYPTIAN ANEBO.
Porphyry to the Prophet Anebo greeting.
I commence my friendship towards you from the Gods and good

dæmons, and from those philosophic disquisitions, which have an
affinity to these powers. And concerning these particulars indeed,
much has been said by the Grecian philosophers; but, for the most
part, the principles of their belief are derived from conjecture.
In the first place, therefore, it is granted that there are Gods. But I
inquire what the peculiarities are of each of the more excellent
genera, by which they are separated from each other; and whether
we must say that the cause of the distinction between them is from
their energies, or their passive motions, or from things that are
consequent, or from their different arrangement with respect to
bodies; as, for instance, from the arrangement of the Gods with
reference to etherial, but of dæmons to aerial, and of souls to
terrestrial, bodies?
I also ask, why, since [all] the Gods dwell in the heavens,
theurgists only invoke the terrestrial and subterranean Gods?
Likewise, how some of the Gods are said to be aquatic and aerial?
And how different Gods are allotted different places, and the parts of
bodies according to circumscription, though they have an infinite,
impartible, and incomprehensible power? How there will be a union
of them with each other, if they are separated by the divisible
circumscriptions of parts, and by the difference of places and subject
bodies?
How do theologists, or those who are wise in divine concerns,
represent the Gods as passive, to whom on this account, it is said,
erect phalli are exhibited, and obscene language is used? But if they
are impassive, the invocations of the Gods will be in vain, which
announce that they can appease the anger of the divinities, and
procure a reconciliation with them; and still more, what are called
the necessities of the Gods, will be vain. For that which is impassive
cannot be allured, nor compelled, nor necessitated. How, therefore,
are many things, in sacred operations, performed to them as passive?
Invocations,—likewise, are made to the Gods as passive; so that not
dæmons only are passive, but the Gods also, conformably to what
Homer says,
“And flexible are e’en the Gods themselves.”[17]
But if we assert with certain persons, that the Gods are pure
intellects, but that dæmons, being psychical, participate of intellect;
in a still greater degree will pure intellects be incapable of being
allured, and will be unmingled with sensible natures. Supplications,
however, are foreign to the purity of intellect, and therefore are not
to be made to it. But the things which are offered [in sacred rites] are
offered as to sensitive and psychical essences.
Are, therefore, the Gods separated from dæmons, through the
former being incorporeal, but the latter corporeal? If, however, the
Gods are incorporeal alone, how will the sun and moon, and the
visible celestials, be Gods?
How, likewise, are some of the Gods beneficent, but others
malefic?
What is it that connects the Gods in the heavens that have bodies,
with the incorporeal Gods?
What is it that distinguishes dæmons from the visible and invisible
Gods, since the visible are connected with the invisible Gods?
In what do a dæmon, hero, and soul, differ from each other? Is it
in essence, or in power, or in energy?
What is the indication of a God, or angel, or archangel, or dæmon,
or a certain archon, or soul being present? For to speak boastingly,
and to exhibit a phantasm of a certain quality, is common to Gods
and dæmons, and to all the more excellent genera. So that the genus
of Gods will in no respect be better than that of dæmons.
Since the ignorance of, and deception about, divine natures is
impiety and impurity, but a scientific knowledge of the Gods is holy
and beneficial, the ignorance of things honourable and beautiful will
be darkness, but the knowledge of them will be light. And the former,
indeed, will fill men with all evils, through the want of erudition, and
through audacity; but the latter will be the cause to them of every
good. [I wish you, therefore, to unfold to me the truth respecting
these particulars.[18]]
[And, in the first place, I wish you to explain to me distinctly[19]]
what that is which is effected in divination? For we frequently obtain
a knowledge of future events through dreams, when we are asleep;
not being, at that time, in a tumultuous ecstasy, for the body is then
quiescent; but we do not apprehend what then takes place, in the
same manner as when we are awake.
But many, through enthusiasm and divine inspiration, predict
future events, and are then in so wakeful a state, as even to energize
according to sense, and yet they are not conscious of the state they
are in, or at least, not so much as they were before.
Some also of those who suffer a mental alienation, energize
enthusiastically on hearing cymbals or drums, or a certain
modulated sound, such as those who are Corybantically inspired,
those who are possessed by Sabazius, and those who are inspired by
the mother of the Gods. But some energize enthusiastically by
drinking water, as the priest of Clarius, in Colophon; others, by being
seated at the mouth of a cavern, as those who prophesy at Delphi;
and others by imbibing the vapour from water, as the prophetesses
in Branchidæ. Some also become enthusiastic by standing on
characters, as those that are filled from the intromission of spirits.
Others, who are conscious what they are doing in other respects, are
divinely inspired according to the phantastic part; some, indeed,
receiving darkness for a cooperator, others certain potions, but
others incantations and compositions: and some energize, according
to the imagination, through water; others in a wall, others in the
open air, and others in the sun, or in some other of the celestial
bodies. Some also establish the art of the investigation of futurity
through the viscera, through birds, and through the stars.
I likewise ask concerning the mode of divination, what it is, and
what the quality by which it is distinguished? All diviners, indeed,
assert, that they obtain a foreknowledge of future events through
Gods or dæmons, and that it is not possible for any others to know
that which is future, than those who are the lords of futurity. I doubt,
therefore, whether divinity is so far subservient to men, as not to be
averse to some becoming diviners from meal.
But, concerning the causes of divination, it is dubious whether a
God, an angel, or a dæmon, or some other power, is present in
manifestations, or divinations, or certain other sacred energies, as is
the case with those powers that are drawn down through you
[priests] by the necessities with which invocation is attended.
Or does the soul assert and imagine these things, and are they, as
some think, the passions of the soul, excited from small incentives?
Or is a certain mixed form of subsistence produced from our soul,
and divine inspiration externally derived?
Hence it must be said, that the soul generates the power which has
an imaginative perception of futurity, through motions of this kind,
or that the things which are adduced from matter constitute
dæmons, through the powers that are inherent in them, and
especially things adduced from the matter which is taken from
animals.
For in sleep, when we are not employed about any thing, we
sometimes obtain a knowledge of the future.
But that a passion of the soul is the cause of divination, is indicated
by this, that the senses are occupied, that fumigations are
introduced, and that invocations are employed; and likewise, that
not all men, but those that are more simple and young, are more
adapted to prediction.
The ecstasy, also, of the reasoning power is the cause of divination,
as is likewise the mania which happens in diseases, or mental
aberration, or a sober and vigilant condition, or suffusions of the
body, or the imaginations excited by diseases, or an ambiguous state
of mind, such as that which takes place between a sober condition
and ecstasy, or the imaginations artificially procured by
enchantment.

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Atmospheric Multiphase Reaction Chemistry 1st

Atmospheric Reaction Chemistry 1st Edition Hajime

Arene chemistry - reaction mechanisms and methods for

Atmospheric Chemistry and Physics: From Air Pollution

The Maillard Reaction in Food Chemistry Current

Paul J Crutzen A Pioneer on Atmospheric Chemistry and

Reaction Engineering 1st Edition Shaofen Li

Multiphase Fluid Flow in Porous and Fractured

Business Cycle Dynamics and Stabilization Policies A

Fundamentals of Secondary Aerosol Formation

Limit of Liability/Disclaimer of Warranty

Library of Congress Cataloging-in-Publication Data

Cover Design: Wiley

Set in 10/12pt WarnockPro by SPi Global, Chennai, India

1 Historical Background of Atmospheric Secondary Aerosol Research 1

2 Fundamentals of Multiphase Chemical Reactions 13

2.3.1.1 Salting-in, Salting-out 38

3 Gas-Phase Reactions Related to Secondary Organic Aerosols 107

3.2.4 Cycloalkenes 139

3.4.3 Monocyclic and Polycyclic Aromatic Hydrocarbons 217

4 Aqueous-Phase Reactions Related to Secondary Organic Aerosols 245

5 Heterogeneous Oxidation Reactions at Organic Aerosol Surfaces 309

5.3 Reactions of Ozone 313

6 Reactions at the Air–Water and Air–Solid Particle Interface 343

6.3.4 Microscopic View of the Interface of Air and Sulfate/Nitrate Aqueous

7 Atmospheric New Particle Formation and Cloud Condensation Nuclei 415

8 Field Observations of Secondary Organic Aerosols453

8.5 Forest Air 465

The ﬁeld of atmospheric multiphase chemistry is still a rapidly developing research

October, 2019 Hajime Akimoto

Historical Background of Atmospheric Secondary Aerosol

1.2 Secondary Inorganic Aerosols

In 1970s, the importance of the reaction of O3 and H2 O2 , formed secondarily in the

1.3 Secondary Organic Aerosols

1.3.1 Photochemical Smog

1.3.2 Blue Haze

Fundamentals of Multiphase Chemical Reactions

2.2 Gas–Liquid Phase Equilibrium and Equilibrium in Liquid

Title: Iamblichus on the mysteries of the Egyptians, Chaldeans,

Translator: Thomas Taylor

Release date: January 29, 2024 [eBook #72815]

Original publication: London: Bertram Dobell & Reeves and

Credits: Richard Tonsing, MFR, and the Online Distributed

*** START OF THE PROJECT GUTENBERG EBOOK IAMBLICHUS

EGYPTIANS, CHALDEANS, AND

TRANSLATED FROM THE GREEK

Ο δε Αριστοτελης προς Αντιπατρον περι Αλεξανδρου γραφων, εφη μη

The various translations and original works of Thomas Taylor,

It appears to me that there are two descriptions of persons by

Porphyry to the Prophet Anebo greeting.

I commence my friendship towards you from the Gods and good

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