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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
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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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Went, F.W. (1960b). Organic matter in the atmosphere, and its possible relation to
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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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place two years before, when stocks began to fail in July and
August, 1845. In the year 1857 commerce and industry expanded
throughout America in increasing volume up to the very eve of the
August crisis, yet the stock market in the summer of the preceding
year gave clear warning of what was to occur. One year before the
panic of 1873 a similar “slump” foretold what was coming, and the
66
same was true of the year preceding the panic of ’93. Previous to
the last-mentioned crisis stocks began to fall, with unmistakable
emphasis, early in 1892. Of seventeen of the most active, five
reached their maximum price in January, 1892, three in February,
four in March, two—Lake Shore and Michigan Central—in April. And
as we have seen, identical preliminary warnings developed on the
Stock Exchange from one year to six months before the last great
67
panic of 1907.
The panic that hit the Paris Bourse in October, 1912, causing a
disturbance not equaled in violence since 1870, was brought about
by sowing the wind through an immense public speculation based on
two fine harvests in Russia and a feverish revival of commercial and
industrial activity all over Europe. Up to this point all the indicia of
the movement—such as bank loans, building operations, public and
private extravagance, and a blind infatuation for speculation by a
normally prudent nation that had not speculated on a large scale
since the Panama débacle of 1894—corresponds exactly with
conditions in America just preceding the 1907 crisis. The similarity
between the two incidents goes even farther, for early in September
of 1912 the French bankers and Agents de Change, recognizing the
strained condition of credit, had deliberately put in motion corrective
agencies designed to stop the rise with the least possible
derangement of confidence.
They would have succeeded, no doubt, and the situation would
have exactly paralleled our own discounting processes of March,
1907, but for the unforeseen Balkan difficulty which, coming out of a
clear sky, upset the plans of the conservative financial forces and
precipitated a panic. It came, as a French banker explained, a week
too soon—by which he meant that, given a little more time, the
worst phases of the disturbance would have been avoided through
gradual and orderly liquidation. As it stands, the panic will no doubt
go down into French financial history as “the Balkan panic,” just as
our disturbance of 1907 is ascribed, faute de mieux, to Wall Street
wickedness; but in reality both the French and American crises had
their origin in precisely similar causes. The Balkan news in Paris only
precipitated what the French Bourse had planned to accomplish in
an orderly manner, just as Wall Street and the Stock Exchange had
done five years earlier in a similar emergency. The essential lesson
of both instances is that the same causes which generate prosperity
will, if pushed far, generate an equivalent adversity.
The details of the panic of 1907 are still fresh in mind, and need
be but briefly referred to. Banks and trust companies closed their
doors and suspended payments to depositors. Cash and credit
became almost unobtainable; we were face to face with
demoralization. Clearing-house certificates were resorted to at
practically all banking centres throughout the country; there was a
general requirement of time notices for withdrawal of savings bank
deposits; all normal credit instruments were impaired. The Secretary
of the Treasury was forced to exercise heroic discretion in the matter
of security for government deposits and for the very necessary
increase of a note circulation that was then suffering from a spasm
of contraction. There was an immense hoarding of funds and a
consequent drying up of fluid capital, while from one end of the
country to the other, there was liquidation, business contraction,
retrenchment, panic, and ruin. “Wall Street” and the Stock Exchange
had foreseen that the chain was only as strong as its weakest link,
and had done what it could to prepare the public for the break. To
assert at this late day that it did aught but its full duty is humbug in
excelsis.
I have already cited one instance, the country’s expanding bank
loans as contrasted with “Wall Street’s” contraction, to show how
plainly the warning was conveyed. As another instance, take the
immobilization of capital tied up in the enormous real-estate
speculation then prevalent. In New York City alone the increase in
mortgages recorded jumped from 455 millions in 1904 to 755
millions in 1905, an increase over the previous years of 32.7 per
68
cent, and 66 per cent, respectively. The figures showing the
increase in building permits are similarly significant, revealing the
fact that in 1905, 1906, and the early months of 1907, money was
pouring into new construction at a rate without precedent. In
Greater New York alone, not including Queens County, building
permits granted in 1904 amounted to $153,300,000, and in 1905 to
$229,500,000, and in the face of disaster this rate of increase
69
continued up to the very eve of the panic.
Outside of New York the expansion in building operations was
equally rapid and equally ominous, showing an increase in twenty-
five cities alone from $201,300,000 in 1903 to $234,200,000 in
1904, to $280,400,000 in 1905 and to $307,800,000 in 1906—all this
but a small part of the actual funds thus locked up throughout the
70
whole country. We thus find that one of the most important and
inevitable causes of the panic was the absorption of exceptionally
large amounts of capital in enterprises that required a considerable
time for completion, or which, when completed, were not
immediately profitable; and to them may be added factories and
extensive public and private works of every kind. This form of
expansion, as Senator Burton points out, when carried to extremes
almost invariably brings about a disturbance.
Now let us consider. Does all this expansion of bank loans
outside of New York and all this tremendous increase of building
operations show that the Samsons of “Wall Street” were pulling
down the temple on their own heads in order to slaughter the
Philistines, as alleged, or does it show an indifference and lack of
readjustment to the growing stringency of money, as revealed by the
Stock Exchange in its liquidation of March and April? “As a rule,” said
John Mill, “panics do not destroy capital; they merely reveal the
extent to which it has been previously destroyed by its betrayal into
71
hopelessly unproductive works.” There would have been no such
“betrayal” had judicious reflection and a measurement of facts
followed Wall Street’s warnings.
A shrewd man, one of the old school of New York City wholesale
merchants, who has nothing whatever to do with Wall Street or the
Stock Exchange, yet whose trade arteries extend to many parts of
the country, has long governed his business by the published reports
of Stock Exchange transactions. If he sees there revealed a
wholesome, normal, and conservative expansion in all lines of
business and a money market that betrays no uneasiness as to the
future, he presses on into new lines of endeavor, confident that the
immediate future is serene. If he finds an urgent liquidation on
’Change, with the coincident phenomena of impaired credit
instruments, he draws in his lines and waits. It makes no difference
to him who is rocking the boat, nor why; experience has taught him
that if it rocks, the time has arrived to go ashore. And this steady old
merchant, I have no doubt, is but one of a numerous type.
Those who ignore the economic tides that ebb and flow through
the medium of the Stock Exchange as they did in 1907, do so
because they do not understand that these great market movements
are really but expressions of natural laws. If there is a rising tide—a
boom—it is attributed by thoughtless people to speculation and
gambling. If there is a bad break, it is caused by panic-stricken
repentant sinners, or by the activities of the bears. The essential
point that is missed here lies in the fact that, while bulls and bears
alike may have their brief hour, sooner or later, regardless of them,
the market responds to actual conditions and discounts the future of
those conditions.
Booms are not made on the Stock Exchange; they are made in
the country’s fields and forests and workshops. Panics are not
created there; they have their origin in mistakes and excesses
throughout the world, and in psychologic conditions which stock
markets cannot hope to control. The pendulum may swing far, but it
comes back. Sooner or later the movement of prices tells the exact
story of future business, and of credit, and of all the economic
agencies that enter into them. This was not well understood in 1907,
and, as I said at the beginning, I doubt if it will ever be understood
in the sense that it will avoid a recurrence of panics. All that we may
hope for is that periods of depression, which are inevitable, may not
be attended in future by such a loss of the reasoning faculties as
that which brought about the affair of 1907.
Now let us consider another cause of the panic—the currency
system, always bearing in mind the fact that the first and greatest
cause of the panic was the over-expansion outside of New York that
has just been described. The causes which we are now to consider
were of minor importance when measured by this overshadowing
matter; nevertheless they played their part and must be considered
accordingly.
Not all panics, to be sure, can be prevented by a perfect
currency system, yet this one could have been measurably
prevented, and “Wall Street” and the Stock Exchange had labored
for years so to prevent it. At the gatherings of the Chamber of
Commerce, at the bank meetings, at all the meetings of merchants
and manufacturers for years preceding 1907, the mischievous effects
of our currency system were proclaimed and the ultimate outcome
predicted. Congress was petitioned again and again to remedy those
intolerable conditions, and to permit national banks to expand their
circulation under proper safeguards, but without avail.
When the storm burst, a most impressive object lesson in
practical finance resulted. What was at worst but a normal
stringency of the circulating medium developed, when added to
abnormal demands from the country at large, into conditions that
created great alarm. There was no way by which the banks of the
country could use the resources which they actually possessed to
meet the urgent requirements of the hour. A great nation of
enterprising people found itself—and still finds itself—compelled to
do a banking business differing in degree, but not in kind, from the
old-woman-and-her-stocking system of finance. The way our
bankers got down on their knees to London and Paris in that
emergency, frankly admitting their inability, under our old flint-lock
laws, to handle a situation which foreign bankers meet without
difficulty, is a subject at once painful and humiliating. Literally our
bankers begged for help and got it. Some day we shall have to beg
again.
Had the national banks of New York City enjoyed the right to
expand their circulation in the manner provided by the plan of the
American Bankers’ Association, at least a part of the débacle would
have been avoided. “The banks and trust companies of this city have
in their vaults the largest store of good credit that can be found in
any city in the world,” said one of America’s foremost economists as
the panic raged, “but much of it is utterly unavailable because of our
currency system. One of the trust companies that closed its doors
has in its possession live assets amounting to over $50,000,000. All
this credit is dead. It cannot do the work of a single dollar in the
paying-teller’s cage. What is wanted in a time like this is freedom to
convert the credit of banks into a medium of payment that will
72
satisfy the people.”
True enough, and just what the whole financial community,
including the Stock Exchange, had been repeating for years.
Currency issues which do not provide for all situations, including not
only ordinary demands, but also such exceptional cases of shrinkage
as this one was, can never be called perfect, nor even safe. There is
73
no health in them. The most effective and the most rapid means of
regulating and protecting the general credit situation is by increasing
or diminishing the volume of outstanding bank-note currency not
covered by a reserve of gold or other lawful money. This method is
employed successfully both in France and in Germany. The Bank of
France and the Imperial Bank of Germany to some extent regulate
credit conditions by acting as central banks of discount; but their
most effective action is by increasing or diminishing the uncovered
amount of their outstanding notes. When additional currency is
needed as a circulating medium they supply this currency by issuing
notes. When contraction of currency, or a check upon the further
expansion of bank credits is desirable, they accomplish the result by
diminishing the volume of their outstanding notes and by raising the
74
discount rate. This system is as nearly perfect as any yet devised.
Whether we shall ever succeed in adopting it, or something like
it, in America, is the burning question in our banking offices to-day.
Until something is done, the layman who distrusts the plan of a
central bank and looks upon Wall Street with abhorrence, may find
satisfaction in knowing that the average New York banker is the
most worried and harassed man in American business life. With
millions of other people’s money in his possession subject to
withdrawal by check at sight, and with millions of the best security in
the world in his vaults lying absolutely idle and worthless so far as
raising currency is concerned, he stands between the devil and the
deep-blue sea. Anything that frightens his depositors, or even
remotely suggests panic, gives him a cold chill. People who talk of
manipulation by New York bankers as a cause of the panic of 1907
or any other panic are blind to the fact that any disturbance of
normal conditions is the one thing that bankers would avoid as they
would avoid the plague.
There was a third cause of the panic in the course pursued by
the President. In some quarters it is still termed “the Roosevelt
panic,” and there exists a belief that the President by his actions and
speeches played a large part in bringing about the crisis. Personally,
I feel that this has been exaggerated. There had been,
unquestionably, wrongdoing by certain corporation managers. The
President, with a characteristic vigor not unknown to politicians,
seized upon it as a theme for his speeches, and the “evils,” the
“malefactors,” the “corruption” and “dishonesty” with which he
bruised the air, raised a suspicion in many quarters as to the status
and security of the whole financial situation and undoubtedly
contributed to the frightened liquidation of the day. The impression
these utterances produced abroad, where American securities were
popular, was painful, and led one returning tourist to remark that
Europe was acquiring the idea that we were “a nation of swindlers.”
All panics are largely psychological, and this was no exception.
The President’s public speeches came at a time when emotion,
apprehension, and alarm filled men’s minds; and at a time when
those irrational moods were most likely to exaggerate the difficulties
that existed, and to conjure up difficulties that did not exist. Panics
seem to come from lack of money, the real difficulty is lack of
confidence, and it was to this that the President’s course directly
contributed.
I am of the opinion that, judged by his public utterances,
especially his October speech at Nashville, Tenn., the President had
not the remotest idea that such an awful shock as the panic of 1907
was imminent. He was not a student of economic conditions; he had
no familiarity with crisis-producing phenomena; he had never seen a
panic at close quarters. His speeches did not cause the panic, for
that disturbance was foreordained; they served, however, to hasten
it, to intensify it, and to keep it alive. Perhaps I may add that the
sparks beaten by him from the anvil of political expediency at that
unfortunate moment threw more light upon the President himself
than upon the evils he condemned. Perhaps, too, that was what the
President most desired. In any case, the fact remains that just as
there is too much confidence in times of excessive expansion, so
there is too little in times of unreasoning depression; and that the
President’s attitude aggravated the latter situations is undeniable.
But by what stretch of the imagination can the Stock Exchange
be credited with playing any part in this third cause of the panic? If
temporary depression results from exposure of wrongdoing among
railroad, industrial, or financial institutions, nowhere in the land is
execration poured forth upon the evil-doers more vigorously than
within its four walls. Far from complaining, the Stock Exchange and
the whole investment community welcome such exposures, despite
their effect on the market, for the precise reason that their own
protection and benefit, if nothing else, is promoted by it.
There was yet another reason for the panic, closely related to
the attitude of the President. I refer to the predicament of the
railways of the country as 1906 passed into 1907. Staggering under
a load of traffic which sorely taxed their equipment, the managers of
these properties cried aloud to the investing public for funds. But
capital was not to be had. Tied up in real-estate speculation and in
quarters whence it could not be easily recovered, the normal supply
of capital was immobile and inert. What was worse, encouraged by
the attitude of the President, an epidemic of radical anti-railroad
legislation became manifest in the several States, new and onerous
burdens of taxation were imposed, and a wave of distrust and
suspicion regarding railway investments was created. Simultaneously
the cost of wages and materials advanced—both characteristic
phenomena indicating trouble—and, as a consequence of all this
blockade, the ratio of net to gross in the matter of increased
earnings fell from the normal proportion of about 40 per cent. in the
first nine months of 1906, to less than 10 per cent. in the same
months of 1907.
Railroads are public utilities that must continue to handle
business offered them no matter what happens, and so, to meet all
these abnormal demands, but one course was left open to them,
and that was to raise funds by issues of new stock. This, of course,
amounted practically to an assessment of stockholders; as an
expedient it failed because “Wall Street” had already recognized the
symptoms of disease. It was too late. Money and credit attract
money and credit, and confidence attracts both. There was a
shocking absence of confidence in the emergency of 1907, and the
railroads suffered enormously by it.
With this matter certainly Wall Street had nothing to do; it could
not in fact do more than it had just done in pointing out to the
country at large, through a drastic process of liquidation, the obvious
withdrawal of far-sighted investors from a situation that had become
tense. Nor can the railroads be censured, because the great volume
of business that confronted them was not created by them, and yet
had to be transported by them. The fault lay, of course, in the
wholesale and reckless expansion of all lines of industry, and in the
immensely increased extravagance of public and private life.
I venture the prediction that when these conditions again
prevail, as they must in a great and vigorous country like ours, the
Stock Exchange will still be found sounding its warnings, but it will
not do to hope that those who learned the bitter lesson of 1907 will
profit by that experience, because the condition of mental
disturbance which is a part of every panic cannot be regulated by
the will, nor kept within bounds by the statute law. The one lesson
we have learned from the predicament of the railroads in 1907 is
that there is a tendency toward disturbance in large accessions
either of business or of capital. “At intervals,” says Walter Bagehot,
“the blind capital of a country is particularly large and craving; it
seeks for some one to devour it, and there is ‘plethora’; it finds some
75
one, and there is ‘speculation’; it is devoured, and there is ‘panic.’”
Summarized briefly, I have attempted to show in the foregoing
pages that the Stock Exchange for many months prior to the panic
had been steadily liquidating and contracting, and had served notice
on the country at large that the time had come to put a stop to the
prevalent over-expansion. It has been demonstrated that instead of
heeding these warnings the general business of the country, as
evidenced by the increases in loans and commercial discounts and
by an over-speculation in real estate and in public and private
extravagances, continued to expand up to the very eve of the panic,
and was stopped then and there only by sheer lack of capital.
Nothing can be of greater importance in any consideration of the
1907 crisis than that its overshadowing cause was the attempt to do
too much business on too little capital, and compared with this all
other aspects of that situation are of minor importance.
I have shown that an antiquated currency system played a
conspicuous part in the crisis, through contributory negligence on
the part of our law-makers. The part played by the President has
been cited as a third, though somewhat negligible, factor in sowing
the seed of distrust, and also the trying position in which the great
common carriers of the country found themselves after the seeds of
distrust had been sown. These were the four causes of the panic of
76
1907.
How well the Stock Exchange did its work in that great
emergency is a matter of record. It did not close its doors; there
were no failures; no relaxation of the protection afforded the public;
no departure from the high standard of morality which is ever its
goal. In one week, ending October 25th, 5,166,560 shares passed
through its hands, representing, with the transactions in bonds, a
par valuation exceeding $483,000,000.
Now, in the very nature of things, a financial panic is the inability
of many debtors to meet their obligations, plus the fear that many
others may be in the same plight. At such a time men hasten to sell
for cash that for which there is the readiest market. Thus they sell
securities because securities are immediately convertible; thus they
turn to the Stock Exchange, because that is what Stock Exchanges
are for. Hence it follows that in a crisis such as that of 1907 the
ruinous decline manifests itself more sharply, and is felt more keenly,
on the Stock Exchange than on the Cotton Exchange or the Produce
Exchange. Men turn to it for first aid to the injured, and the greater
the casualty list, the more marked is the disturbance of values. That
this is not well understood by the public often unfortunately leads to
suggestions of improper methods where none exist.
Finally, where do we stand? Orthodox economists like Wells talk
of over-production as a cause of panics; currency experts bewail a
lack of circulating media; theorists of the school of Jevons are driven
to seek in sun-spots the potent force of all our harvests; Levi and
Mill dwell upon the periodicity of panics and would fix their
appearance by schedules of time; politicians and thinkers-in-embryo
point the finger at Wall Street, and yet, with all that has been
written, thirteen great crises at home and abroad within the last
century show that we have not begun to get at these disturbances.
Drought has been a cause of mischief, yet we have learned to
irrigate and to conserve; epidemics have smitten us, yet we have
mastered sanitation; floods have ruined whole territories, yet we
have built dikes and levees. But every now and then, when business
seems to be at its best, when merchants are dividing large profits,
and when labor is best rewarded, a panic occurs and the whole
structure collapses.
To say that Wall Street or Lombard Street or any group of men
anywhere can bring such conditions to pass is to deny all the facts of
experience. Depressions may come from any of a hundred causes,
but panics originate in the mind; they are manias. Walter Bagehot
gave up trying to prescribe for them because he realized that sudden
frenzy is not an ailment to be foreseen and prevented. “But one
thing is certain,” he said, “that at particular times a great many
stupid people have a great deal of stupid money;” to which he adds,
“our scheme is not to allow any man to have a hundred pounds who
cannot prove to the Lord Chancellor that he knows what to do with a
hundred pounds.” When thousands of people ignore all the warnings
of experience, as they always will do; when with a blind misdirection
of energy they sink borrowed capital in quagmires at fancy prices, as
they always have done; and when, shorn of their all, they are
simultaneously seized with a mania to denounce others for the
consequences of their own folly, as they always must do, one cannot
avoid the thought that perhaps Bagehot’s humorous solution is the
77
best that has been devised.
CHAPTER VII
A BRIEF HISTORY OF LEGISLATIVE ATTEMPTS

TO RESTRAIN OR SUPPRESS SPECULATION
In the Middle Ages the notion prevailed that there was a just and
equitable price for everything, and that any person who tried to
obtain more than this price was a sinner. Trade for gain was
anathema; the man who bought the principal commodities of that
time, such as corn or herrings, with a view to selling them at a
profit, was guilty of “craft and sublety”—as the old English statutes
read—that infallibly cost him his goods and brought him to the
pillory. Thus in the year 1311 one Thomas Lespicer of Portsmouth
was caught red-handed in London with six pots of Nantes lampreys
stored in a fishmonger’s cellar in the hope of a rising market. The
law required that when he arrived in London from Portsmouth with
his lampreys he should proceed to the open market under the wall
of St. Margaret’s Church in Bridge Street, and stand there four days
selling at current prices to any one who cared to buy. His failure to
do so, and his wickedness in attempting to “bull” the lamprey market
by hiding them in the fishmonger’s cellar, resulted in the arrest of
himself and the fishmonger, and their trial and punishment at the
hands of the Mayor and Alderman.
Professor W. T. Ashley, who cites this incident in his
“Introduction to English Economic History and Theory” (London
1892), also gives another instance in which our modern theories of
natural rights and freedom of contract seem to be in hopeless
conflict. John-at-Wood, a baker, was arrested in 1364 charged with
the profane practice of “bulling” wheat. “Whereas one Robert de
Cawode,” the indictment reads, “had two quarters of wheat for sale
in common market on the pavement within Newgate; he, the said
John, cunningly and by secret words whispering in his ear,
fraudulently withdrew Cawode out of the common market, and they
went together into the Church of the Friars Minor, and there John
bought the two quarters at 15½d per bushel, being 2½d over the
common selling price at that time in the market, to the great loss
and deceit of the common people, and to the increase of the
dearness of wheat.” At-Wood denied this heinous offence and “put
himself on the country,” whereupon a jury was empanelled, which
gave a verdict that At-Wood had not only thus bought the grain, but
that he had afterward returned to the market and boasted of his
crime, and “this he said and did to increase the dearness of wheat.”
Accordingly he was sentenced to be put in the pillory for three
hours, and one of the sheriffs was directed to see the sentence
executed and proclamation made of the cause of the punishment.
So far as I am aware the Statutes of Henry III and Edward I,
under which these culprits were punished, constitute the earliest
official attempts to repress speculation by law. After the Revolution,
the Bank of England having been organized and bank shares
created, a speculative outburst occurred that led to the enactment of
fresh legislation entitled “An act to restrain the numbers and ill
78
practices of brokers and stock-jobbers,” but this law lapsed or was
repealed ten years later. In 1707 a law was passed licensing brokers
79
and making it unlawful for unlicensed brokers to do business, and
in 1708 City rules were established for brokers, obliging them to give
bonds for the proper performance of their duties. In 1711, 1713, and
1719, laws were enacted similar to the Act of 1707.
Then came the speculative schemes of 1720, of which the most
famous or infamous was the South Sea Company, designed to make
fortunes for its shareholders in the slave-trade and in whale fishing.
It was followed by many other projects almost fantastic in their
wildness to each of which the public subscribed liberally. Where all
the money came from that kept this disastrous speculative mania
alive is something one would like to know. There seems to have
been no limit to it. South Sea shares stood at 120 in April of 1720; in
July they had reached 1020, and, after that, the collapse. The
company became a “bubble,” and a burst one at that—and a great
popular outcry followed. It resulted, in 1734, in the passage of Sir
John Barnard’s “Act to Prevent the Infamous Practice of Stock-
Jobbing,” the preamble reciting:
“Whereas, great inconveniences have arisen, and do daily

arise, by the wicked, pernicious, and destructive practice of
stock-jobbing, whereby many of His Majesty’s good subjects
have been and are diverted from pursuing and exercising
their lawful trades and vocations to the utter ruin of
themselves and their families, to the great discouragement of
industry, and to the manifest detriment of trade and
commerce.”
This act forbade bargains for puts and calls, and also “the evil
practice of compounding or making up differences”; but its principal
provision was the prohibition of short selling under penalty of £100
for each transaction. There was, of course, an appeal to the courts,
which held that the statute did not apply to foreign stocks nor to
shares in companies, but only to English public stocks, a decision
that effectually put an end to the usefulness of the law. It remained
on the statute books, however, and it was occasionally resorted to
by persons who sought to evade the fulfillment of their speculative
contracts—a class of persons known to-day as “welchers.”
Finally, in 1860, the law was repealed altogether, the repeal act
reciting that Sir John Barnard’s Act “imposed unnecessary
restrictions on the making of contracts for sale, and transfer of
public stocks and securities.” Thus the first serious attempt to
regulate speculation in securities by law, and specifically to prohibit
short selling, came to be recognized as a failure by the frank
admission of government. In 1867 the so-called Leeman Act became
law, prohibiting all sales of bank stock unless the numbers of the
certificates sold were specified—an attempt to prevent short selling
of bank stock. Even this law was subsequently repealed, and
England, to-day, has no law on the statute books restricting
speculation.
As the London Stock Exchange grew in influence and
importance, reflecting England’s development as the world’s banker,
popular attack and criticism continued to assail it. It may be frankly
admitted that the legitimate functions of the institution had been
abused by foolish or unscrupulous persons, just as every important
branch of business and politics has been misused, the world over,
since civilization began. The question therefore arose whether these
occasional sharp practices proved the Exchange to be an
excrescence on the body politic, or whether, on the other hand, its
importance in the mechanism of modern business merely required
improvements and reforms. In this situation, which occurred in 1877,
and which caused considerable agitation on the part of both parties
to the controversy, a royal commission was appointed “to inquire
into the origin, objects, present constitution, customs, and usages of
the London Stock Exchange.” The Exchange and its critics thus
reached the parting of the ways. A year was spent by the
commission in examining witnesses and conducting investigations
along special lines, and in 1878 its report, with the evidence, was
published in a Parliamentary Blue Book.
The report absolutely upheld the purposes and functions of the
Stock Exchange and the legitimacy of speculation in securities, and it
went further in pointing out the danger of attempting to force any
form of external control on the institution. The evils of that form of
Stock Exchange speculation which closely approaches mere
gambling were plainly stated, and the report suggested that the
Exchange authorities restrain such practice in so far as was possible.
As the conclusions of the royal commission are of very great
importance, marking as they do the first serious official study in
modern times of the Stock Exchange theory, I quote from the Blue
Book in the hope that Stock Exchange critics of to-day may
understand how these conclusions were reached. “In the main,”
reads the report, “the existence of the Stock Exchange and the
coercive action of the rules which it enforces upon the transaction of
business and upon the conduct of its members has been salutary to
the interests of the public. We wish to express our conviction that
any external control which might be introduced by such a change
should be exercised with a sparing hand. The existing body of rules
and regulations have been formed with much care, and are the
result of the long experience and vigilant attention of a body of
persons intimately acquainted with the needs and exigencies of the
community for whom they have legislated. Any attempt to reduce
this rule to the limits of the ordinary laws of the land, or to abolish
all checks and safeguards not to be found in that law, would, in our
opinion, be detrimental to the honest and efficient control of
business.”
In 1909 similar criticism in New York having led to the
appointment of the Hughes Commission to inquire “what changes, if
any, are advisable in the laws of the State bearing upon speculation
in securities and commodities, or relating to the protection of
investors, or with regard to the instrumentalities and organizations
used in dealings in securities and commodities, which are the subject
of speculation,” the commission reported to the Governor, after six
months of laborious investigation, in these words:
“Speculation in some form is a necessary incident of

productive operation. When carried on in connection with
either commodities or securities it tends to steady their
prices. Where speculation is free, fluctuations in prices,
otherwise violent and disastrous, ordinarily become gradual
and comparatively harmless. For the merchant or
manufacturer speculation performs a service which has the
effect of insurance. The most fruitful policy will be found in
measures which will lessen speculation by persons not
qualified to engage in it. In carrying out such a policy
exchanges can accomplish more than legislation. We are
unable to see how a State could distinguish by law between
proper and improper transactions, since the forms and the
mechanisms used are identical. Rigid statutes directed against
the latter would seriously interfere with the former.
Purchasing securities on margin is as legitimate a transaction
as the purchase of any property in which part payment is
deferred. We, therefore, see no reason whatsoever for
recommending the radical change suggested that margin
trading be prohibited.”
Here are two reports at an interval of thirty-one years, made by

independent investigators of high character, concerning the two
foremost Stock Exchanges in the world. Both of these reports
recommend changes and improvements, and each is firmly of
opinion that the changes recommended are such as can be carried
out by the Stock Exchanges themselves without the assistance or
interference of the legislature.
As the London Stock Exchange is a voluntary association similar
to that in New York, it was inevitable that the question of
incorporation should have been brought before the royal commission
of 1877, and that the question as to whether the public interest
would be promoted by such incorporation should be given careful
attention. As a result of these deliberations, a majority of the
commission recommended that the London Stock Exchange should
voluntarily apply for a royal charter or act of incorporation, but the
reasons upon which this recommendation were based had to do with
the temporary or shifting character of the membership, which gave
very little assurance to the public of the permanence and stability of
the rules, since members of the London Stock Exchange are only
elected for one year. It need scarcely be added that such an
argument would not apply to the New York Stock Exchange.
Now it so happened that, despite this opinion by the royal
commission, the London Exchange was not compelled to
incorporate, and remains to-day a purely voluntary association or
club. The reason for this lies, in large measure, in the very intelligent
minority opinions filed with the Board’s report by those of its
members who dissented from the recommendation. As this is a
matter of interest to members and friends of the New York Stock
Exchange, I give herewith the substance of these dissenting
opinions, calling the reader’s attention to the fact that the Hughes
Commission of 1909 rejected similar proposals regarding the New
80
York Stock Exchange. The Hon. Edward Stanhope, M. P., said,
regarding the proposed application for a charter:
“Supposing such an application to be made, and

Parliament to be prepared to incorporate the Stock Exchange
on the terms which are embodied in the report, the
consequence would be that rules so established would be
stereotyped, and could only be altered, even in the minutest
details, with the approval of a department of the State. In my
opinion this requirement would be either mischievous or
nugatory. To attempt to regulate the manner in which
business is conducted in the great money market of England
is going far beyond the province of the State, nor is any
government department in any way qualified to undertake it.
The report, indeed, recommends that external control should
be exercised with a sparing hand. But experience seems to
show that the first commercial crisis, or the discovery of any
gigantic fraud, would cause a pressure for further restrictions
which the department entrusted with these duties could not
possibly withstand. If incorporation is to be anything more
than a theory, it seems to me that it must either be imposed
compulsory upon the Stock Exchange, or it must be offered to
them on terms which will make it worth their while to accept
it. The first alternative I reject, for the reason given by the
select committee on foreign loans, that it would destroy that
freedom which is the life and soul of the institution. If,
however, any voluntary scheme commends itself to the
opinion of the Stock Exchange, its primary condition should
be to reserve to that body absolute liberty in the transaction
of their ordinary business (as to which we are all of opinion
that, speaking generally, no just fault can reasonably be
found), and also the power of adapting their rules, with the
utmost ease and freedom, to the varying wants of the time.”
Mr. S. R. Scott of the dissenting minority was even more

emphatic in his objections to incorporation. He said:
“In fixing my name to this report, I desire to make the

reservations following: 1. With regard to incorporation, I
object to recommend it for the following reasons: Hitherto,
the Stock Exchange has been carried on with great success as
a voluntary association, and has had a vigorous growth. It
has not enjoyed a single legal privilege, yet it has thriven and
the public have neglected more than one effort to establish
an open market to resort to it for business, and to give it
exclusive confidence. This royal commission has been sitting
more than twelve months, yet no important or reliable
evidence has been volunteered of a character adverse to the
general practices or conduct of business on the Stock
Exchange. If proof be required that the internal legislation
and administration of the Stock Exchange enforce a higher
standard of morality than the law can reach or enacts for the
regulation of other trades, such proof is to be found in the
fact that recently the committee of the Stock Exchange were
assailed at law by a member whom they expelled on a charge
of dishonorable conduct, the lawsuit being based on the
ground that the action of the committee was not justified in
law. The trial lasted seven days and proved abortive, the
distinction between the standard enforced by the committee
and the statutory provisions of the law not being appreciated
by the special jury promiscuously selected from various
trades, although quite intelligible to the judge. In maintaining
this high standard the committee are compelled to go beyond
the common law, binding their members to the observance of
their rules and practices, even though not enforceable in a
court of law. If, however, they should submit to incorporation,
their rules would have to be assimilated to the law, and their
freedom of action would be curtailed—results which might
tend to cripple them in sustaining the standard alluded to,
and operate in many ways as a hindrance to that rapidity of
action which is an absolute necessity in critical times. Further,
incorporation implies, in some sort, monopoly, and it remains
to be proved that the public would gain by any restriction of
the freedom of trade, even in stocks and shares. I adhere to
the opinion expressed in 1875 by the Committee on Foreign
Loans, on page 47 of their report, as follows: ‘That such a
body (the Stock Exchange) can be hardly interfered with by
Parliament without losing that freedom of self-government
which is the only life and soul of business.’”
As I have outlined elsewhere in this volume the cogent

objections to incorporation of the New York Stock Exchange, it only
remains to say here that the great argument against such a step
consists in the Governing Committee’s absolute power of summary
discipline over the members, a power that greatly exceeds the
authority of the common law, and one that protects the patrons of
the Exchange to an extent that would not be possible if, under
incorporation, members could invoke their constitutional
81
prerogatives. Said the governors in reply to a question of the
Hughes Commission: “Appeals to the courts have been rare,
considering the number of cases in which such power of discipline
has been exercised, but we may well cite as substantiating in an
extraordinary degree the fairness and right-mindedness with which
members have been held to their obligations, the fact that, although
in a number of instances appeals have been made to the courts for
reinstatement by members who have been expelled or suspended
for infraction of the rules, or for conduct which, although it might
not be in violation of any express rule or regulation, or in violation of
any law or legal obligation, the committee have held to be
inconsistent with the maintenance and exercise of those standards
of honorable dealing which it is the function of the Exchange to
inculcate and maintain; nevertheless, in the last twenty-eight years
there has not been a single instance of the judgment of the
Governing Committee being reversed by the courts.”
The distinction between the expulsion of a member of such a
voluntary unincorporated association and the expulsion or removal of
a member of a corporation is very important. The moment the body
receives a charter a different set of principles comes into play as
82
regulating the relations between the member and the body.
Germany dealt with a similar situation in very different fashion.
In the autumn of 1891 there were disastrous failures of certain
German banking houses, resulting from criminal misuse of bank
deposits and from an undue participation in speculative transactions
by the general public. The outcry that followed was no new thing in
Germany, for as early as 1888 conditions that had arisen in the
Berlin market and the Hamburg coffee market had led to petitions to
the Reichstag demanding remedies for speculative evils. The
cumulative effect of these difficulties was such that, as related by
Doctor Loeb, bills directed against speculation on the Exchanges
were introduced in November, 1891. “As early as February 16, 1892,”
according to this authority, “the Chancellor of the Empire appointed
a commission of inquiry of twenty-eight members, most of them
lawyers, but with representation also of landed proprietors,
economists, and merchants. The chairman was the President of the
Directorate of the Reichbank, Doctor Koch. The commission began
its inquiries in April, 1892, held 93 sessions, and summoned 115
witnesses, of whom the great majority were persons engaged in the
transactions which it was proposed to regulate. The commission also
made inquiries as to the state of legislation and trade usages in the
several states of the Empire and in foreign countries.
“The commission presented a majority report on November 11,
1893, recommending certain statutory and administrative changes.
The principles on which these recommendations rested was that, in
view of the importance of the interests which were represented at
the Exchanges, modifications should be made with caution, and the
existing complicated trade usages and methods should not be
disregarded; while, on the other hand, there was no occasion for
regarding with mistrust, still less with hostility, interference in the
83
free working of industrial forces.”
Up to this point, it will be observed, the German investigators
followed precisely the same lines as the English Commission of 1877
and the Hughes Commission of 1909. Mistakes are recognized, but
modifications are to be made “with caution.” But it so happened that
the recommendations in this respect were not followed. German
politics at that time were in a state of turmoil in consequence of the
Agrarian agitation, and in the various phases of political expediency
that attended the uproar, first the government and then the
Reichstag insisted upon more and more stringent enactments
concerning legislation against the Exchange, until finally a hostile law
was enacted quite out of line with the original recommendations of
the committee of inquiry. In other words, the politicians ignored the
labors of the committee and took matters into their own hands. The
three important provisions of this law were these:
(1) All exchange dealings for future delivery in grain and

flour were forbidden.
(2) All exchange dealings for “the account” in the shares
of mining and industrial companies forbidden.
(3) An “Exchange Register” was established in which was
to be entered the name of every person who wished to
engage in exchange transactions for future delivery. Contracts
made by two persons entered in the register were declared
binding and exempt from the defence of wager.
The immediate effect of this law on the German grain market

was disastrous. Futures were not suppressed. The grain trade was
simply forced by the law to give up the modern machinery that
experience had developed, and go back to antiquated forms of
dealing. “It was like taking machinery out of a mill,” says Frank
Fayant, “and putting manufacture back to hand labor.” As to trading
in securities “for the account,” here, too, the law failed utterly. Even
the government—at that time most unfriendly to the Exchanges—
admitted in its official reports that the law had “proved injurious to
the public,” and that “the dangers of speculation have increased.”
We have high authority for a detailed examination of the disaster
attending this costly experiment in the remarks of Professor Emery,
who tells us not merely how the German law failed, but why:
(1) Fluctuations in prices have been increased rather than

diminished. The corrective influence of the bear side of the
market having been restricted, the tendency to an inflated
bull movement was increased in times of prosperity. This in
turn made the danger of radical collapse all the greater in
proportion as the bull movement was abnormal. The greater
funds needed to carry stocks on a cash basis further
increased the danger when collapse was threatened. The
result was an increased incentive to reckless speculation and
manipulation. Says the report of 1907, “The dangers of
speculation have been increased, the power of the market to
resist one-sided movements has been weakened, and the
possibilities of misusing inside information have been
enlarged.”
(2) The money market has been increasingly demoralized
through the greater fluctuations in demand for funds to carry
speculative cash accounts. The New York method is held in
abhorrence by German financiers, who attribute to it, in large
part, the wild fluctuations in New York call rates, the frequent
“money panics” and the tendency to reckless “jobbery.” In
proportion as the new Berlin methods approached the cash
delivery system of New York, these evils have appeared there.
(3) The business of the great banks has been increased
at the expense of their smaller rivals. The prohibition of
trading for the account made it difficult for the latter to carry
out customer’s orders because the new methods required
large supplies of both cash and securities. Furthermore, an
increasing share of the business of the large banks came to
be settled by offsets among their customers, and the actual
exchange transactions became a proportionally small part of
the total transfers.
(4) This has a twofold effect. Business within the banks is
done on the basis of exchange prices, but these became
more fluctuating and subject to manipulation as the quantity
of exchange dealings were diminished and were concentrated
in a few hands. The advantages of a broad open market were
lost. The object of the act had been to lessen the speculative
influence over industrial undertakings. Its effect was to
increase it.
(5) Finally, the effect of interference, increased cost, and
legal uncertainty was to drive business to foreign exchanges
and diminish the power of the Berlin Exchange in the field of
international finance. The number of agencies of foreign
houses increased four or five fold and much German capital
flowed into other centres, especially London, for investment
or speculation. This in turn weakened the power of the Berlin
money market, so that even the Reichbank has at times felt
84
its serious effects.
Concerning the “Exchange Register” (which the government has

now abolished as a complete failure) and the effort to keep the
public out of the speculative markets, Professor Emery says:
In one sense the fate of the famous exchange register is

laughable, but in a deeper sense it is genuinely sad, for the
object was a worthy one and the new scheme was adopted
with high hopes. Its failure was inevitable, since it did not
remove the temptation to speculate. The men who felt this
temptation most, and whose position least warranted their
yielding to it, were of course the very last men to have
themselves registered. In fact the whole public revolted. The
number of registrations never reached four hundred, which
number would not begin to cover the banking and brokerage
concerns. The number of “Outsiders” registered never
reached forty. Even the conservative banks had to choose
between giving up all such business and dealing with non-
registered parties.
(1) The uncertainties of the new situation were most
likely to exclude the cautious and well-to-do from
participation in the market. The reckless gambler of small
means was less likely to be disturbed in his practices.
(2) The act aimed to establish legal certainty by means of
registration. It proved a direct incentive to fraud. The
customer was not legally liable on his contracts; therefore,
every reckless and dishonest little plunger, who could get a
broker to trust him, could take a “flyer” with everything to
gain and nothing to lose. Cases increased rapidly in the courts
and the worst element of the public was active to the relative
exclusion of the better. Instances even occurred where a man
would play both sides of the market at the offices of two
different brokers and simply refuse to settle on the losing
contract.
(3) As affecting this phase of the question, references
should be made again to the transfer of business to foreign
exchanges. Morally and socially it is as bad for the German
public to speculate in cheap mining stocks on the London
Exchange as to do so at home. The flow of German funds into
the market for South African securities would indicate a
further way in which the purposes of the act were defeated.
(4) Finally, the question must be faced of the effect of
eliminating the public from the speculative market even if it
could be accomplished. It is supposed sometimes that such a
result would be all benefit and no injury. On the contrary, the
real and important function of speculation in the field of
business can only be performed by a broad and open market.
Though no one would defend individual cases of recklessness
or fail to lament the disaster and crime sometimes
engendered, the fact remains that a “purely professional
market” is not the kind of market which best fulfills the
service of speculation. A broad market with the participation
of an intelligent and responsible public is necessary. A narrow
professional market is less serviceable to legitimate
investment and trade and much more susceptible of
85
manipulation.
It is not surprising that such a law, enacted to meet political

clamor, in defiance of the recommendations of the committee, and in
the face of all the economic experiences of the century, should have
proved a fiasco in a double sense. Not only did it fail to accomplish
its purpose, but, as we have seen, it brought about a new chain of
evils vastly more distressing to German commercial development
than all the evils that gave it birth. The report of the Deutsche Bank
for 1900 said: “The prices of all industrial securities have fallen. This
decline has been felt all the more as, by reason of the ill-conceived
Bourse Law, it struck the public with full force without being
softened through covering purchases of speculative interests.” Four
years later the same bank reported: “A serious political surprise
would cause the worst panic, because there are no longer any
dealers to take up the securities which, at such times, are thrown
upon the market by the speculating public.” In 1905 the bank again
forcibly urged the revision of the law in these words:
“In our last report we referred to the great danger which may be
brought about through delaying the revision of the Bourse Laws, and
we are now pointing to it again because we consider it our duty to
impress again and again a wider circle of the public with the
economic value of the Stock Exchange and its important relation to
our financial preparedness in times of war.”
Again, the following year the bank kept pounding away on the
same theme: “If it had still been necessary to furnish proof of the
regrettable fact that the German Bourses are no longer able to
accomplish their task—equally important to the welfare of the people
as to the standing of the Empire—the trend of events during the
past financial year in general, and the result of the last German
Government issues in particular, would have furnished that proof.”
Meanwhile, other leading financial institutions took up the same
cry. Thus the Dresdner Bank in its report in 1899 said: “The danger
which lies in the ban put on speculation, especially in the prohibition
of trading for future delivery in mining and industrial securities, will
become manifest to the public, if, with a change of economic
conditions, the unavoidable selling force cannot be met by dealers
willing and able to buy. It will then be too late to recognize the
harmful effects of the Bourse Law.” In 1902 the Disconto-
Gesellschaft reports: “The unfortunate Bourse Laws continue to be a
grave obstacle to business activity.” And again in 1903: “The Bourse
will not be able to resume its important economic functions until the
86
restrictions upon trading for future delivery have been removed.”
The lesson to be learned from the failure of the German Bourse
Law of 1896, and from the frank recognition of that failure as
evidenced by the repeal of 1908, cannot be overestimated in its
importance. It is inconceivable that law-makers of to-day may ignore
such a warning. I have quoted freely from Professor Emery of Yale
University in pointing out the deplorable results of that legislation
because his study of the subject has made him the foremost
authority. The remonstrances of the German banks and business
men have also been cited because they were on the spot; they saw
and felt the prostration of German business that followed swiftly on
the heels of this law; they were a unit in pronouncing it a wretched
failure. In the appendix to this work will be found the report of the
Hughes Commission in which the ten experts on that board
unanimously reported “the evil consequences” of Germany’s
experiment, its “grotesque” operation in practice, and its utter
failure.
It is a simple matter for the querulous and discontented element
of a community to reason along the lines of least resistance and
demand the enactment of laws to right every fancied wrong. But the
patient study of such matters, the nice balancing of probabilities, the
penetrating investigation of similar experiments elsewhere and the
analysis of their bearing on the larger affairs affected by them—all
this requires critical judgment of a high order. When such an issue is
evolved laymen stand aside for a while, until the evidence of experts
has been submitted to minds competent to decide in accordance
with evidence.
Applying this principle to the ever-present menace of legislation
in America directed against the Stock Exchange, we find each
witness testifying to the fact that the German law of 1896, far from
benefiting the public, injured it immeasurably. It put a premium on
reckless speculation and offensive manipulation; it demoralized the
money market; it choked the small banks and made virtual
monopolies of the large ones; just in proportion as it stifled
speculation it put an end to industrial undertakings that depend for
their success upon the spirit of adventure and risk; it drove money
and credit out of Germany and into London and Paris; it removed
from the Berlin market the support of the bears, thus exposing the
whole investment structure to violent collapse. The layman must
consider this and the men who make our laws must look before they
leap.
Speculators in the region of criticism, whether of theology or
economics, who find themselves face to face with a fact too
stubborn to fit in with their opinions or conclusions, have but two
courses open to them: either to reconsider in the light of testimony
the conclusions they have reached, or to denounce and discredit the
inconvenient witness. In this instance the inconvenient witness
cannot be denounced; his name is legion. Every merchant in
Germany will tell you the Bourse Law was a sad mistake and will
deplore its enactment. Nor can such witnesses be discredited;
therefore the advocate who believes that in legislation lies the
remedy for what he conceives to be the evils of speculation must
perforce choose the other horn of the dilemma; he must reconsider.
It is a gratifying fact that in America, where law-makers are
prone to enact a hodge-podge of laws on every conceivable subject,
there has been no such serious mistake made by the Federal
Government as that which occurred in Germany. In 1812, five years
before the New York Stock Exchange was organized, an act was
passed by the New York State Legislature entitled “An act to regulate
sales at public auction and to prevent stock-jobbing,” its essential
purpose being the prevention of short selling—the bête-noir of all
the early amateurs in economics. This was the only anti-speculation
act ever placed on the New York Statute books. The act read:
That all contracts, written or verbal, hereafter to be

made, for the sale or transfer, and all wagers concerning the
prices, present or future, of any certificate or evidence of
debt due by or from the United States or any separate State,
or any share or shares of stock of any bank, or any share or
shares of stock of any company, established or to be
established by any law of the United States, or any individual
State, shall be, and such contracts are hereby declared to be,
absolutely void, and both parties are hereby discharged from
the lien and obligation of such contract or wager; unless the
party contracting to sell and transfer the same shall at the
time of making such contract be in actual possession of the
certificate or other evidence of such debt or debts, share or
shares, or to be otherwise entitled in his own right, or duly
authorized or empowered by some person so entitled to
transfer said certificate, evidence, debt or debts, share or
shares so to be contracted for. And the party or parties who
may have paid any premium, differences or sums of money in
pursuance of any contract, hereby declared to be void, shall

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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

A BRIEF HISTORY OF LEGISLATIVE ATTEMPTS

“Whereas, great inconveniences have arisen, and do daily

“Speculation in some form is a necessary incident of

Here are two reports at an interval of thirty-one years, made by

“Supposing such an application to be made, and

Mr. S. R. Scott of the dissenting minority was even more

“In fixing my name to this report, I desire to make the

As I have outlined elsewhere in this volume the cogent

(1) All exchange dealings for future delivery in grain and

The immediate effect of this law on the German grain market

(1) Fluctuations in prices have been increased rather than

Concerning the “Exchange Register” (which the government has

In one sense the fate of the famous exchange register is

It is not surprising that such a law, enacted to meet political

That all contracts, written or verbal, hereafter to be

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