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Chemistry of Pyrotechnics
Chemistry of ­Pyrotechnics
Basic Principles and ­Theory

Third Edition

John A. Conkling and Christopher J. Mocella

CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742

© 2019 by Taylor & Francis Group, LLC

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Contents
Preface to the Third Edition: 2019.............................................................................xi
Preface to the Second Edition: 2010....................................................................... xiii
Preface to the First Edition: 1985............................................................................. xv
Authors....................................................................................................................xvii

Chapter 1 Introduction...........................................................................................1
A Primer on Energetic Materials..........................................................1
Black Powder: The Original Pyrotechnic.............................................3
A Brief History and Cultural Significance............................................5

Chapter 2 Basic Chemical Principles.....................................................................9

Atoms and Molecules............................................................................9
The Mole Concept............................................................................... 17
Electron Transfer Reactions................................................................ 19
Oxidation–Reduction Theory......................................................... 19
The Pyro Valence Method: A Simple Yet Powerful Technique..... 21
Balancing an Equation...................................................................24
Is a Chemical Compound Fuel or Oxygen Rich?...........................25
Weight Ratio Calculations..............................................................26
Analyzing the Pyro Valence of a Mixture...................................... 27
Three-Component Systems............................................................ 27
Pyro Valence Exercises..................................................................28
Additional Pyro Valence Problems................................................ 31
Electrochemistry................................................................................. 32
Thermodynamics.................................................................................34
Introduction to Thermodynamics...................................................34
Heat of Reaction............................................................................. 36
Rates of Chemical Reactions.............................................................. 39
Energy-Rich Bonds............................................................................. 42
States of Matter................................................................................... 43
Gases..............................................................................................44
Liquids............................................................................................ 45
The Solid State...............................................................................46
Other Phases of Matter................................................................... 48
Acids and Bases................................................................................... 48
Light Emission.................................................................................... 50
Molecular Emission........................................................................ 53
“Black Body” Radiation/Emission................................................. 54
“Green” Chemistry and Pyrotechnics: An Introduction..................... 54
Chemical Principles: A Final Note..................................................... 55

v
vi Contents

Chapter 3 Components of Energetic Compositions............................................. 57

Introduction......................................................................................... 58
Oxidizing Agents................................................................................60
Requirements..................................................................................60
Potassium Nitrate (KNO3)..............................................................64
Potassium Chlorate (KClO3)...........................................................64
Potassium Perchlorate (KClO4)...................................................... 68
Green Pyrotechnics: The Perchlorate Issue.................................... 69
Ammonium Perchlorate (NH4ClO4)............................................... 71
Ammonium Perchlorate in the News............................................. 72
Dinitramides: A “Green” Replacement for Perchlorates?.............. 73
Periodates: A “Green” Replacement for Perchlorates?.................. 74
5-Aminotetrazole: A “Green” Replacement for Perchlorates?....... 75
Strontium Nitrate [Sr(NO3)2].......................................................... 75
Barium Nitrate [Ba(NO3)2]............................................................. 76
Iron Oxide [Fe2O3 and Fe3O4]......................................................... 76
Other Oxidizers.............................................................................. 77
Oxidizers without Oxygen.............................................................. 78
Summary on Oxidizers and Their Use........................................... 78
Oxidizer Selection: A Comparison................................................ 79
Fuels.................................................................................................... 79
Requirements.................................................................................. 79
Introduction to Metal Fuels............................................................ 81
Aluminum (Al)............................................................................... 83
Magnesium (Mg)............................................................................84
Recovery of Demilitarized Magnesium: “Green”
Pyrotechnics Recycling.................................................................. 85
“Magnalium” (Magnesium–Aluminum Alloy).............................. 85
Iron (Fe).......................................................................................... 86
Other Metals................................................................................... 86
Introduction to Non-Metallic/Elemental Fuels.............................. 87
Sulfur.............................................................................................. 87
Boron.............................................................................................. 89
Silicon.............................................................................................90
Phosphorus..................................................................................... 91
Sulfide Compounds........................................................................92
Introduction to Organic Fuels.........................................................92
Natural Organic Fuels: Shellac and Red Gum...............................94
Charcoal.........................................................................................94
Carbohydrates................................................................................. 95
Other Organic Fuels.......................................................................96
Binders................................................................................................97
An Overview of Binders.................................................................97
Most Binders Are Also Fuels....................................................... 101
Contents vii

Retardants.......................................................................................... 102
Brief Note on Colored Dyes......................................................... 103
Catalysts............................................................................................ 104
Gas Volume Considerations: A Review............................................ 104
Examples...................................................................................... 105
Conclusion and Best Practices in Component Selection................... 105

Chapter 4 Pyrotechnic Principles...................................................................... 107

Introduction....................................................................................... 107
Technical Parameters for Pyrotechnic Behavior............................... 108
Variability of Pyrotechnic Compositions.......................................... 113
Requirements for a “Good” High-Energy Mixture........................... 119
Preparation of High-Energy Mixtures: An Introduction.................. 121
Variation from Day to Day................................................................ 122
Possible Areas Where Variation in the Performance and
Sensitivity of Pyrotechnic Mixtures Can Occur During the
Manufacturing Process................................................................. 123
Aging Effects on Pyrotechnic Compositions.................................... 124
Pyrotechnic Principles: A Final Note............................................... 125

Chapter 5 Pyrotechnic Laboratories and Analysis............................................ 127

Introduction....................................................................................... 128
The Pyrotechnic Laboratory............................................................. 128
Storage.......................................................................................... 129
Safety: Personal Protective Equipment and Common Practices.....131
Composition Production.................................................................... 132
Sizing Particles and Powders........................................................ 133
Measuring Chemicals................................................................... 135
Mixing the Compositions............................................................. 136
Using the Laboratory Hood “Firing Range”..................................... 137
Setting Up the Lab Hood/Firing Range....................................... 137
Igniting the Composition.............................................................. 138
Cleanup and a Final Note on Safety............................................. 139
Analysis and Pyrotechnics................................................................ 139
Introduction to Analysis of Pyrotechnic Compositions............... 139
Thermal Analysis......................................................................... 140
Heat Output Measurement............................................................ 144
Spectroscopy................................................................................. 144
Microscopy................................................................................... 145
Moisture Analyzer........................................................................ 145
Other Equipment and Techniques................................................ 145
Process Hazard Analysis................................................................... 146
Laboratories and Analysis: A Final Note.......................................... 146
viii Contents

Chapter 6 Ignition and Propagation................................................................... 147

Introduction to Ignition Principles.................................................... 148
Ignition Techniques...................................................................... 148
Ignition: Initial and Continuing Events........................................ 149
Combustion, Deflagration, and Detonation.................................. 149
Ignition Factors: Part 1................................................................. 150
Lattice Structure, Motion, Reactivity, and “The Tammann
Temperature”................................................................................ 152
Ignition Factors: Part 2................................................................. 153
Ignition Temperatures................................................................... 157
Methods for Determining Ignition Temperatures........................ 158
Summary of Ignition.................................................................... 161
Propagation of Burning..................................................................... 161
Introduction and Measuring Propagation..................................... 161
Effects from Component Selection............................................... 162
Effects from Mass Ratio and Stoichiometry................................ 163
Effect from Other Factors: Heat Transfer, Loading Density,
and Moisture................................................................................. 164
Effect of External Pressure and Confinement.............................. 165
Effect of External Temperature.................................................... 168
Burning Surface Area................................................................... 169
Deflagration-to-Detonation Transitions (DDT)............................ 170
Summary of Burn Rate................................................................ 171
Combustion Flame Temperature....................................................... 171
Propagation Index............................................................................. 175
Ignition and Propagation: A Final Note............................................ 176

Chapter 7 Sensitivity.......................................................................................... 177

Sensitivity Testing: An Introduction................................................. 177
Ignition Sensitivity: A Statistical Event........................................ 178
Sensitivity Testing: Safety Concerns............................................ 179
Variability in Sensitivity Testing Results..................................... 180
Spark Sensitivity................................................................................ 181
Friction Sensitivity............................................................................ 184
Impact Sensitivity.............................................................................. 186
Thermal Sensitivity........................................................................... 189
Thermal Sensitivity Overview...................................................... 189
Divergent Sensitivity Changes...................................................... 192
Shock Sensitivity: A Brief Note........................................................ 193
Redesigning a Composition for Sensitivity Considerations.............. 194
Pyrotechnic Sensitivity: Summary.................................................... 195

Chapter 8 Heat Compositions: Ignition Mixes, Delays, and Thermites............ 197

Heat Production................................................................................. 198
Contents ix

Igniters and Delays: Terminology..................................................... 198

Ignition Compositions and First Fires............................................... 201
Delay Compositions..........................................................................204
Thermodynamics and Delay Compositions.................................206
Stoichiometry and Delay Compositions.......................................207
“Green Pyrotechnics” for Delay Systems.....................................209
Thermite and Thermate Mixtures..................................................... 210
Heat Compositions: Summary.......................................................... 212

Chapter 9 Propellants: A Brief Overview.......................................................... 213

Propellants: An Introduction............................................................. 214
The Original Propellant: Black Powder............................................ 215
Smokeless Powders............................................................................ 216
Propellants for Launch Vehicles....................................................... 220
Projectile vs. Rocket Propellants....................................................... 221
Modern Approaches in Propellants................................................... 222

Chapter 10 Light and Color Production............................................................... 225

Introduction....................................................................................... 225
White-Light Compositions................................................................ 226
Overview of White-Light Production........................................... 226
Illuminating Compositions and Flares......................................... 227
“Photoflash” Mixtures ................................................................. 230
“Green Pyrotechnics” for Photoflash Compositions.................... 231
Spark Production............................................................................... 231
Strobes and “Twinklers”................................................................... 233
Other Light Effects: Flitter and Glitter............................................. 234
Colored-Light Production.................................................................. 235
Overview of Colored-Light Production........................................ 235
Oxidizer Selection ....................................................................... 238
Fuels and Burning Rates ............................................................. 239
The Veline Color Series................................................................240
Color Intensification with Chlorine..............................................240
Red Flame Compositions: Classic Strontium-Based Systems...... 242
Red Flame Compositions: Lithium-Based Alternatives............... 243
Green Flame Compositions: Classic Barium-Based Systems...... 245
Green Flame Compositions: “Green Pyrotechnics” with
Boron-Based Compositions..........................................................248
Blue Flame Compositions: Classic Copper Chloride-Based
Systems.........................................................................................248
Blue Flame Compositions: “Green Pyrotechnics” with
Copper Iodide and Copper Bromide............................................ 251
Purple Flame Compositions ........................................................ 251
Yellow Flame Compositions: Sodium.......................................... 252
x Contents

Sodium Impurities: A Caution in Color Production..................... 253

Orange Flame Compositions: Calcium and Sodium/
Strontium Combinations...............................................................254
Infrared Emission and Pyrotechnics................................................. 254
Light and Color Production: Summary............................................. 256

Chapter 11 Smoke Production............................................................................. 257

Introduction....................................................................................... 257
Generation and Dispersion of Solid Particles............................... 258
Vaporization of Volatiles.............................................................. 259
Colored-Smoke Mixes....................................................................... 259
Overview of Colored-Smoke Production..................................... 259
Green Pyrotechnics: An Environmentally Benign Yellow
Smoke........................................................................................... 262
White Smoke Production..................................................................264
Overview of White Smoke Production.........................................264
“Green Pyrotechnics”: HC Smoke Replacement Research.......... 267
Summary: The Challenge and Opportunity of Smokes.................... 269

Chapter 12 Sound Production.............................................................................. 271

Noise Production: Reports................................................................ 271
Whistles............................................................................................. 274
Crackle Effects.................................................................................. 275
A Final Note on Studying the Chemistry of Pyrotechnics............... 277

Chapter 13 Acknowledgments and Further Exploration..................................... 279

Acknowledgments and Thanks......................................................... 279
Further Resources for Exploring Pyrotechnics.................................280

References.............................................................................................................. 283
Index....................................................................................................................... 291
Preface to the Third
Edition: 2019
This book is a continuation of the lifelong work and dedication of Dr. John Conkling,
whom I have had the distinct honor to work for. While Dr. Conkling has “retired”
from primary work on The Chemistry of Pyrotechnics, the reader should make no
mistake that this is still entirely his work, and his are the shoulders that I stand on.
I met Dr. Conkling in 1999 while working at Washington College in Chestertown,
MD (both our alma mater) between school years as I worked for the summer con-
ferences held there, one of which was his legendary Summer Pyrotechnics Seminar.
At that time a good friend of mine was also his research fellow and, seeing the
opportunity, I inquired and later became Dr. Conkling’s summer research fellow.
I completed my undergraduate research under his tutelage, concurrently becoming
a member of the pyrotechnics seminar instructional staff, and continued through
its final 27th year in 2010. Dr. Conkling continues to advise on this project and
many other pyrotechnics and fireworks ventures out there, and I cannot express my
gratitude enough for his mentorship, both academic and professional, and continued
friendship to this day.
In continuing Dr. Conkling’s work with this text, I have strived to take the core
discussion of chemistry and pyrotechnics and update the main themes with recent
advancements since the previous version was published, most notably in the world
of “green pyrotechnics” and finding new formulations with decreased toxic effects
to humans and the environment around us. The amount of research going into new
pyrotechnic study is extensive, and I was able to include only a small segment of
what is out there. I hope the reader will be inspired to use the many references and
ideas to continue their own research and advance the state-of-the-art of pyrotechnics
well into the 21st century.

Christopher J. Mocella
Annapolis, MD

xi
Preface to the Second
Edition: 2010
In the twenty-five years that have passed since the first edition of this book was
­published, the world of pyrotechnics and high energy materials has continued to
undergo significant changes. The changes have been driven primarily by concerns
for safety - of personnel working with energetic materials, of the communities
located near facilities producing energetic materials, as well as concerns for the
environment. One result of the pressure for change has been the promulgation of
new government regulations placing restrictions on the materials that may be used
in energetic mixtures, mandating numerous training programs, and initiating other
actions - such as OSHA’s Process Safety Management Standard - intended to elim-
inate accidents and incidents. And almost all of the personnel who entered the field
of energetic materials in the 1950’s and 1960’s have now retired and taken with
them their years of hands-on, practical knowledge in the preparation of energetic
mixtures.
The International Pyrotechnics Seminars have grown in frequency and signif-
icance since the first edition of this book was published in 1985. There is now at
least one seminar a year, either in Colorado or a non-United States location, and
the proceedings from these seminars continue to be a great source of information
regarding ongoing pyrotechnic research. In addition, the International Symposium
on Fireworks (ISF) continues to be held every other year in Canada or elsewhere and
these sessions always produce an interesting blend of technical papers.
The Pyrotechnics Guild International (PGI) has matured into a respected group
of pyrotechnics enthusiasts and researchers who are making significant contribu-
tions in the area of fireworks technology.
A new journal, appropriately named The Journal of Pyrotechnics, has provided
a vehicle for the prompt publication of research and review papers in the broad field
of pyrotechnics.
On the negative side, we in the United States continue to lack any organized,
broad-range academic programs covering the science of energetic materials. The
New Mexico Institute of Technology is offering a program in explosive technology,
and this is a great first step. More and more, the field of pyrotechnics is interacting
with and adapting to changing technology in areas such as obscuration science and
low-signature flame emission. Greater academic interest in the science of pyrotech-
nics would be a valuable asset for this country.
I’d like to thank my numerous colleagues and co-workers over the past twenty-­five
years for their interesting discussions, helpful comments, and constructive ­criticism.
First on the list is Joseph Domanico, my friend and colleague with the Summer
Pyrotechnic Seminar program at Washington College since 1984 – Joe is truly a
unique individual with a broad knowledge of the field of energetic materials.

xiii
xiv Preface to the Second Edition: 2010

I also want to thank Christopher J. Mocella, Washington College ‘01 for his assis-
tance with, and contributions to, the second addition of this book. Chris also partic-
ipates as an instructor in the Summer Pyrotechnic Seminars at Washington College,
and has become a valuable member of the team.
The thank-you list includes Tom Shook and Loy Aikman at Pine Bluff Arsenal,
who got me involved in the military side of pyrotechnics two decades ago. Another
special acknowledgement goes to David Pier of MP Associates, with whom I have
enjoyed debating a wide variety of topics covering many aspects of energetic material
for many years. Other friends and colleagues who have contributed to my education
include the late Fred McIntyre, and another former Washington College chemistry
student Jeff Johnson, with Orion Safety Products. I’d also like to thank the American
Pyrotechnics Association for allowing me time to pursue my scientific interests for
many years, and to TNT Fireworks and Orion Safety Products for allowing me to
assist them with interesting projects since my retirement for the APA. More thanks
go to the participants in my Summer Pyrotechnic Seminar programs for the past 27
years, and to my friends at the Bureau of Alcohol, Tobacco and Firearms, and Judy
LeDoux and Debra Satkowiak in particular, for allowing me to assist them with
training for their personnel.
Finally, I must acknowledge the importance of my wife Sandra to this proj-
ect, without whose persistent encouragement this second edition would have been
delayed even more. Aiding her in this motivational effort have been my two children,
Melinda Conkling Hart and John A. Conkling, Jr., who in addition have presented us
with four wonderful Texas grandchildren – John Maxey Hart, Edward Austin Hart,
Jr., Julia Valliant Conkling, and the newest arrival John A. Conkling III. Maybe one
of them will go on to a career in this fascinating field.
This book continues to stress basic chemical principles, rather than serve as a
“how-to” guide for pyrotechnics. There are detailed published works covering many
areas of energetic materials in detail. This book is intended as a bridge to allow
people to transition with confidence from a knowledge of chemistry to an ability to
apply chemical principles and logic to energetic materials. Discussion of the histor-
ical past of the field of pyrotechnics is, regrettably, kept to a minimum. The history
of this field - particularly the work in the 20th century - is another book waiting for
someone to pursue, but there should be no doubt in anyone’s mind that pyrotechnics -
like any other field of science - can only grow and expand as a science by building on
past accomplishments in the field. Everyone’s goal must continue to be to make the
field of energetic materials as productive and useful, and as safe, as we possibly can.

John A. Conkling
Chestertown, MD
Preface to the First
Edition: 1985
Everyone has observed chemical reactions involving pyrotechnic mixtures. Beautiful
4th of July fireworks, highway distress signals, solid fuel boosters for the Space
Shuttle, and the black powder used by muzzle-loading rifle enthusiasts all have a
common technical background.
The chemical principles underlying these high-energy materials have been
­somewhat neglected in the twentieth century by academic and industrial researchers.
Most of the recent work has been goal-oriented rather than fundamental in nature
(e.g., produce a deeper green flame). Many of the significant results are found in
military reports, and chemical fundamentals must be gleaned from many pages of
test results.
Much of today’s knowledge is carried in the heads of experienced personnel. Many
of these workers acquired their initial training during World War II, and they are
presently fast approaching (if not already past) retirement age. This is most unfortu-
nate for future researchers. Newcomers have a difficult time acquiring the skills and
the knowledge needed to begin productive experiments. A background in chemistry
is helpful, but much of today’s modern chemistry curriculum will never be used by
someone working in pyrotechnics and explosives. Further, the critical ­education in
how to safely mix, handle, and store high-energy materials is not ­covered at all in
today’s schools and must be acquired in “on-the-job” training.
This book is an attempt to provide an introduction to the basic principles of
high-energy chemistry to newcomers and to serve as a review for experienced per-
sonnel. It can by no means substitute for the essential “hands on” experience and
training necessary to safely work in the field, but I hope that it will be a helpful
companion. An attempt has been made to keep chemical theory simple and directly
applicable to pyrotechnics and explosives. The level approaches that of an intro-
ductory college course, and study of this text may prepare persons to attend profes-
sional meetings and seminars dealing with high-energy materials and enable them
to intelligently follow the material being presented. In particular, the International
Pyrotechnic Seminars, hosted biannually in the United States by the Illinois Institute
of Technology Research Institute in conjunction with the International Pyrotechnics
Society, have played a major role in bringing researchers together to discuss current
work. The Proceedings of the nine seminars held to date contain a wealth of infor-
mation that can be read and contemplated by persons with adequate introduction to
the field of high-energy chemistry.
I would like to express my appreciation to Mr. Richard Seltzer of the American
Chemical Society and to Dr. Maurits Dekker of Marcel Dekker, Inc. for their encour-
agement and their willingness to recognize pyrotechnics as a legitimate branch of
modern chemistry. I am grateful to Washington College for a sabbatical leave in 1983
that enabled me to finalize the manuscript. I would also like to express my thanks

xv
xvi Preface to the First Edition: 1985

to many colleagues in the field of pyrotechnics who have provided me with data
as well as encouragement and to my 1983 and 1984 Summer Chemistry Seminar
groups at Washington College for their review of draft versions of this book. I also
appreciate the support and encouragement given to me by my wife and children as I
­concentrated on this effort.
Finally, I must acknowledge the many years of friendship and collaboration that
I enjoyed with Mr. Joseph H. McLain, former Chemistry Department Chairman and
subsequently President of Washington College. It was his enthusiasm and encourage-
ment that dragged me away from the norbornyl cation and physical organic chemistry
into the fascinating realm of pyrotechnics and explosives. The field of high-energy
chemistry lost an important leader when Dr. McLain passed away in 1981.

John A. Conkling
Chestertown, MD
Authors
Dr. John A. Conkling  received his BSc degree from Washington College in
Chestertown, Maryland, in 1965 and his PhD in chemistry from Johns Hopkins
University in 1969. Dr. Conkling returned to Washington College as a chemistry
professor and colleague of Dr. Joseph McLain, who at the time was studying ener-
getic materials and pyrotechnics, which Dr. Conkling began to study for his career.
As former executive director and technical director of the American Pyrotechnics
Association, Dr. Conkling is widely regarded as one of the world’s foremost experts
in pyrotechnics. Dr. Conkling conducted “The Summer Pyrotechnic Seminar”
at Washington College for 29 years, and he is the original author of Chemistry of
Pyrotechnics: Basic Principles and Theory in 1985 and second edition in 2010.
Dr. Conkling retired from Washington College in 2012 and was awarded the Alumni
Service Award in 2013. Dr. Conkling currently splits his time between Chestertown
and Texas to be with his family.

Christopher J. Mocella received his BSc degree in chemistry from Washington

College in Chestertown, Maryland, in 2001, having studied as a research associate
under Dr. John Conkling. Chris continued to work with Dr. Conkling at his Summer
Pyrotechnics Seminar series and assisted with the second edition of the Chemistry
of Pyrotechnics text. Following graduate studies in chemistry at the University of
Virginia, Chris took a position as a chemist with the U.S. federal g­ overnment where
he continues his career today. Chris lives with his wife and son near Annapolis,
Maryland.

xvii
 1 Introduction

Red, white, and blue bursts highlight at 4th of July fireworks spectacular.

Welcome to the world of energetic materials. Few people plan to spend their
professional careers in this field of science and technology, but there is an old
saying that “once you smell the smoke,” you are hooked.

A PRIMER ON ENERGETIC MATERIALS

This book is an introduction to the basic principles and theory of pyrotechnics, with
a focus on the chemistry and chemical interactions of the materials involved.
The term “pyrotechnics” comes from the Greek noun pyr for “a fire,” and techne
for “art,” “craft skill,” or “technique,” which today might also be thought of as “sci-
ence.” Therefore, we might think of pyrotechnics as the “art of fire” or the “science
of fire” and, as the reader will see, both scientific principles as well as some artistic
creativity go into all pyrotechnic work.
Much of the “pyrotechnics” material in this text is also applicable to the closely
related areas of propellants and explosives, all of which fall under the broad umbrella
of “energetic materials” as shown in Figure 1.1. Propellants are designed to “defla-
grate,” or burn considerably rapidly—but not quite explode—under the confinement
of a rocket engine or a gun barrel (noting that many propellants burn rather mildly

1
2 Chemistry of Pyrotechnics

ENERGETIC MATERIALS

Propellants Explosives Pyrotechnics

“Move things” “Damage/destroy things” “Do all the other things”

• Rockets • Commercial explosives • Fireworks
• Munitions • Mining • Smokes
• Other projectiles • Demolition • Heating
• Military explosives • Colored flame
• Lights/flares
• Delays/fuses
• Salute/sound
• Welding
• Too many to list!

FIGURE 1.1 This chart shows a breakout of the disciplines of “energetic materials,” classi-
fied as propellants (which move objects), explosives (which damage or destroy objects), and
pyrotechnics (which is a catch-all for the many other functions that energetic materials can
perform). While one could consider propellants and explosives types of pyrotechnics, the
breadth and depth of the applications and study going into each affords them categories all
their own.

in the open when unconfined). Propellants are formulated to maximize the volume
of hot gas produced as the propellant material rapidly burns, pushing the hot gas out
and, hopefully, the projectile in the intended direction. Explosives rapidly release
large amounts of energy, and explosives engineers take advantage of this rapid
release of energy, and the associated shock and pressure, to do work, often through
a full “detonation” event (the difference between deflagrations and detonations will
be discussed in a later chapter).
Pyrotechnic mixtures, our primary interest here, usually (but not always) react
more slowly than explosive or propellant compounds, and the heat generated by the
burning chemical mixture is used to produce combinations of light, color, smoke,
gas, heat, and noise for a wide range of applications. Pyrotechnics, additionally, will
combust as a smolder, as a fast burn, or as a full “deflagration” as opposed to a nearly
instantaneous “detonation” of high explosives. Notably, a well-established research
journal by the name Propellants, Explosives, Pyrotechnics has been publishing
peer-reviewed research since 1976. The terms “high-energy chemistry” and “ener-
getic materials” are also used to refer to these three closely related fields as a group.
The chemical reactions involved in pyrotechnics are of the classic electron-­transfer
or oxidation-reduction type (also colloquially referred to as “redox” reactions). Here,
chemical species interact, exchange electrons, form new products, and release any
excess energy. The mixtures to be studied are almost always solids at room tempera-
ture and are designed to function in the absence of external oxygen. Table 1.1 illus-
trates the reaction rates to be dealt with in that range along a continuum from very
Introduction 3

TABLE 1.1
Classes of “High-Energy” Reactions
Approximate
Class Reaction Velocity Example
Burning Millimeters per second Delay mixtures, colored smoke compositions
(mm/s)
Deflagration Meters per second (m/s) Rocket propellants, confined black powder
Low-order detonation >1 Kilometer per second Dynamite, TNT
(km/s)
High-order detonation >5 km/s Military explosives

slow burning to “instantaneous” detonations with rates greater than a kilometer/sec-

ond. We should note that “detonation” refers to a specific, shock-­propagated process
for the reaction of an energetic material—the term “detonation” is not synonymous
with “ignition” or “explosion.” A detonation is an explosion, but so are high-rate
deflagrations (especially when the material is confined).1

BLACK POWDER: THE ORIGINAL PYROTECHNIC

It is important to recognize early on that the same material may vary dramatically
in its reactivity depending on its method of preparation and the conditions under
which it is used. Black powder is an excellent example of this variability, and it is quite
­fitting that it serves as the first example of a “high-energy material” due to its historical
significance (Kelly 2004; Buchanan 1996). Black powder is an intimate mixture of
potassium nitrate (∼75% by weight), charcoal (∼15%), and sulfur (∼10%), and its unique
properties and characteristics continue to intrigue researchers even today (Brown and
Rugunanan 1989; Hussain and Rees 1992; Maltitz 2001). A reactive black powder is
no simple material to prepare and is a classic example of the “art” of manufacturing
pyrotechnics. If one gently mixes the proper ratio of three components briefly, a pow-
der is produced that is difficult to light and burns quite slowly. The same ingredients in
the same proportions—when thoroughly mixed, moistened, and ground with a heavy
stone wheel to achieve a high degree of homogeneity—become a mixture that readily
ignites and burns rapidly. Particle size, purity of the starting materials, mixing time,
and a variety of other factors—including the type of wood used to prepare charcoal—
are all critical in producing high-performance black powder. Also, deviations from the
75/15/10 ratio of ingredients will lead to substantial changes in performance. Much of
the early history of modern Europe is related to the availability of high-quality black
powder for use in rifles and cannons. A good black powder manufacturer was essential
to military success although he usually received far less recognition and decoration
than the generals who used his product in their battles.
The burning behavior of black powder illustrates how a pyrotechnic mixture
can vary in performance depending on the conditions of its use. A small pile of

1
All detonations are explosions, but not all explosions are detonations!
4 Chemistry of Pyrotechnics

loose black powder can be readily ignited by the flame of a match, producing an
orange flash and a puff of smoke—but almost no noise. The same powder, tightly
sealed in a strong paper tube but still in loose condition, will explode upon ignition
by means of a fuse, rupturing the container with an audible noise. Black powder
spread in a thin trail will quickly burn along the trail, a property used in making
early fuses. Finally, if the powder is compressed in a tube, one end is left open, and
that end is then constricted to partially confine the hot gases produced when the
powder is ignited, a rocket-type device is produced. This varied behavior depend-
ing on confinement is quite typical of pyrotechnic mixtures and illustrates why one
must be quite specific in giving instructions for preparing and using the materials
discussed in this book.
Black powder is also a good example to use to illustrate the dramatic effect that
moisture can have on pyrotechnic compositions. Damp powder is difficult to light
and burns quite slowly—if at all—if ignition is successful. “Keep your powder dry”
is still among the best pieces of advice for anyone making or using pyrotechnic
materials, and hygroscopic chemicals—those that tend to rapidly pick up moisture
in a humid environment—tend to be avoided by pyrotechnic formulators or kept in
tight containers in environmentally controlled locations.
Why should someone working in pyrotechnics and related areas bother to study
the basic chemistry involved? Throughout the 400-year “modern” history of the
United States, many black powder factories have been constructed and put into oper-
ation. Although “smokeless powder” (a general term for propellants with more gas-
eous and less particulate combustion products than black powder, most commonly
nitrocellulose-based) and other new materials have replaced black powder as a pro-
pellant and delay mixture in many applications, there is still a sizeable demand for
black powder in both the military and civilian pyrotechnic industries due to its inex-
pensive ingredients and consistent properties when consistently prepared and stored.
How many black powder factories are still operating in the United States today?
Exactly one—GOEX Powder Inc., in Louisiana (GOEX, Inc. 2014). The remainder
have been destroyed by explosions or closed because of the probability of one occur-
ring: costs associated with critical worker safety are unable to compete economically
with factories in other countries that are not subject to strict safety requirements, a
potentially dangerous trade. In spite of a demand for the product, manufacturers
are reluctant to engage in the production of the material because of the history of
problems with accidental ignition during the manufacturing process. Why is black
powder so sensitive to ignition? What can the chemist do to minimize the hazard?
Can one alter the performance of black powder by varying the ingredients and their
percentages, using theory as the approach rather than trial-and-error?
Black powder is not unique in its properties, however. High-energy materials
like propellants and pyrotechnics are all designed to release energy in brief peri-
ods of time when an ignition stimulus is applied. New formulations continue to be
developed, and new materials continue to be investigated for possible use in novel
compositions. A pyrotechnic formulation consisting largely of magnesium powder
and polytetrafluoroethylene (PTFE, also the chemical in the DuPont company’s
Teflon® product) is used to produce decoy flares for the protection of military air-
craft from heat-seeking missiles. This material has acquired a “black powder”-like
Introduction 5

reputation in recent years. Virtually every manufacturer of this material has suffered
an incident producing magnesium-Teflon® composition, and the need to understand
the basic science of the material has received much attention (Kubota and Serizawa
1987; Kuwahara, Matsuo and Shinozaki 1997). It is this type of problem and its
analysis that we hope can be addressed a bit more thoroughly and scientifically with
an understanding of the fundamental concepts presented in this book. If one accident
can be prevented as a consequence of someone’s better insight into the chemical
nature of high-energy materials, achieved through study of this book, then the effort
that went into its preparation was worthwhile.

A BRIEF HISTORY AND CULTURAL SIGNIFICANCE

The use of chemicals and chemical mixtures to produce heat, light, smoke, noise,
and motion has existed for several thousand years, originating most likely in China
or India. India has been cited as a particularly good possibility due to the natural
deposits of saltpeter (potassium nitrate, KNO3) found there (U.S. Army Material
Command 1967).
Much of the early use of chemical energy involved military applications. “Greek
fire,” first reported in the 7th century AD, was probably a blend of sulfur, organic
fuels, and saltpeter that generated flames and dense fumes when ignited. It was used
in a variety of incendiary ways in both sea and land battles and added a new dimen-
sion to military science (U.S. Army Material Command 1967).
At some early time, most likely prior to 1000 AD, an observant scientist rec-
ognized the unique properties of a blend of potassium nitrate (“saltpeter”), sulfur
(“brimstone”), and charcoal. Black powder was developed as the first “modern”
high-energy composition. One interesting conjecture is that Chinese experimenters
were searching for an elixir for immortality by mixing the “yin” of potassium nitrate
and the “yang” of sulfur to create a “fire drug” (McLain 2017).
The Chinese were involved in pyrotechnics at an early date and had developed
rockets by the 10th century (U.S. Army Material Command 1967) and were using
black powder filled bamboo sticks thrown into fires to ward off evil spirits (McLain
2017). Fireworks followed, including firecrackers, and Chinese firecrackers became
a popular item in the United States when trade was begun between the United States
and China in the 1800s. Family correspondence passed down to Dr. John Conkling,
the primary author of this book, shows that his great-great-grandfather, a merchant
ship captain also named John Alexander Conkling, included “firecrackers” on his
personal shopping list for a voyage to Canton, China (now Guangdong, China) in
the 1830s. Dr. Conkling was not aware of this until after he had himself become
involved in the field of pyrotechnics but was pleased to learn that the Conkling fam-
ily was among the first importers of Chinese fireworks into the United States.
Chinese fireworks remain popular in the United States today, along with an
assortment of other types of pyrotechnic articles that produce a wide assortment of
visible and audible effects. The Japanese also produce beautiful fireworks, but, curi-
ously, they do not appear to have developed the necessary technology until fireworks
were brought to Japan around 1600 AD by an English visitor (Shimizu 1981). Many
of the advances in fireworks technology over the past several centuries have come
6 Chemistry of Pyrotechnics

from these two Asian nations, and China today is the world’s primary supplier of
both consumer and display fireworks.
The use of pyrotechnic and propellant mixtures for military purposes in rifles,
rockets, flares, and cannons developed simultaneously with the civilian applications
such as fireworks. Progress in both areas followed advances in modern chemistry, as
new chemical compounds were isolated and synthesized and became available com-
mercially to the pyrotechnician. Berthollet’s discovery of potassium chlorate in the
1780s resulted in the ability to produce brilliant flame colors using pyrotechnic com-
positions, and color was added to the effects of sparks, noise, and motion p­ reviously
available using potassium nitrate-based compositions.
The harnessing of electricity led to the manufacturing of magnesium and alu-
minum metals by electrolysis in the latter part of the 19th century, and bright white
sparks and whiter light could then be produced. Strontium, barium, and copper com-
pounds capable of producing vivid red, green, and blue flames also became commer-
cially available during the 19th century, and modern pyrotechnic technology really
took off.
Simultaneously, the discovery of nitroglycerine in 1846 by Sobrero in Italy, and
Nobel’s subsequent work with dynamite, led to the development of a new generation
of true high explosives that were far superior to black powder for many blasting
and explosives applications. These materials released their chemical energy through
the detonation process, at rates much faster—and with greater accompanying blast
pressure and shock—than the deflagration process by which propellants and pyro-
technics react upon ignition. The development of modern smokeless powder in the
latter part of the 19th century—based on nitrocellulose and nitroglycerine—led to
the demise of black powder as the main propellant for guns of all types and sizes.
Although black powder has been replaced in most of its former uses by newer
and more energetic materials, it is important to recognize the important role black
powder has played in modern civilization. Tenney Davis, addressing this issue in his
classic book on the chemistry of explosives, wrote, “The discovery that a mixture of
potassium nitrate, charcoal, and sulfur is capable of doing useful work is one of the
most important chemical discoveries or inventions of all times... the discovery of the
controllable force of gunpowder, which made huge engineering achievements pos-
sible, gave access to coal and to minerals within the earth, and brought on directly
the age of iron and steel and with it the era of machines and of rapid transportation
and communication” (Davis 1941). Black powder remains a viable energetic material
today—it ignites readily and reliably and is quite stable in storage if kept dry, and
it is commercially available in a range of grain sizes ranging from fine powder to
granules the size of kernels of corn. Black powder is also fascinating because it is one
of the very few materials produced by the chemical industry that is still made today
using essentially the same materials and manufacturing process as it was produced
500 years ago.
Explosives are widely used today throughout the world for mining, excavation,
demolition, and military purposes. Pyrotechnics are also widely used by the military
for signaling, obscuration, and training simulators. Military technology is constantly
striving to keep pace with advances in other areas of technology, such as thermal
detection and “night vision” equipment. Civilian applications of pyrotechnics are
Introduction 7

many and varied, ranging from the common match to highway warning flares
(“fusees”) to ever-popular fireworks and the spectacular “special effects” used to
enhance movies, rock concerts, professional wrestling matches, sporting events, and
theme park shows.
The fireworks industry remains perhaps the most visible example of pyrotechnics
to the general public and also remains a major user of traditional black powder. This
industry provides the pyrotechnician with the opportunity to fully display his skill at pro-
ducing colors and other brilliant visual effects. The use of fireworks in the United States
has not diminished. There has been a steady growth in consumption of fireworks from
an estimated 30 million pounds in 1976 to over 285 million pounds in 2015, according to
data compiled by the American Pyrotechnics Association (APA 2017).
Fireworks form a unique part of cultural heritage of many countries (Plimpton
1984). In the United States, fireworks have traditionally been associated with
Independence Day—The Fourth of July. In England, large quantities are set off in
commemoration of Guy Fawkes Day (November 5th), while the French use fireworks
around Bastille Day (July 14th). Many countries use fireworks to celebrate the New
Year on January 1st. Notably, in Germany, the use of fireworks by the public is
limited to one hour per year: from midnight to 01:00 a.m. on January 1st—but it is
reported to be quite a celebration. Much of the Chinese culture is associated with the
use of firecrackers to celebrate New Year’s and other important occasions, and this
custom has been carried over to the Chinese communities throughout the world. The
brilliant colors and booming noises of fireworks appear to have a universal appeal
to our basic senses, eliciting “ooh’s” and “aah’s” from spectators regardless of where
the fireworks are displayed—worldwide.
To gain an understanding of how these beautiful effects are produced, we will
begin with a review of some basic chemical principles and then proceed to discuss
various pyrotechnic systems.
 2 Basic Chemical Principles

BLACK POWDER GRANULES: Black powder granules—the first commercial energetic

material that has remained an article of commerce for over 1,000 years. This unique blend of
potassium nitrate (saltpeter), charcoal, and sulfur (brimstone) has served as an explosive, a
propellant, and a component in pyrotechnic devices such as safety fuses and squibs.

Most chemistry courses do not discuss energetic materials—explosives, pro-

pellants, and pyrotechnics—directly or by name. However, these materials
all involve “chemistry in action” and produce their energetic output through
chemical reactions. Many of the principles and logical thought processes that
are taught in “Chem 101” directly apply to what will be covered in this book.
Pyrotechnics are not magic, and the pyrotechnic chemist is no longer viewed
as a wizard. When you are working in this field, and things seem to be making
no sense, it’s time to go back to the basics of science.

ATOMS AND MOLECULES

To understand the chemical nature of pyrotechnics and other energetic mixtures,
one must begin at the atomic level. Two hundred years of elegant experiments and
complex calculations have led to our present picture of the atom as the fundamental
building block of matter. An atom consists of a small, dense nucleus containing

9
10 Chemistry of Pyrotechnics

TABLE 2.1
Properties of the Subatomic Particles
Particle Location Charge Mass, a.m.u.a Mass, grams
Proton In nucleus +1 1.007 1.673 × 10−24
Neutron In nucleus 0 1.009 1.675 × 10−24
Electron Outside nucleus −1 0.00549 9.11 × 10−28

a
a.m.u. = atomic mass unit, where 1 a.m.u. = 1.66 × 10−24 g.

positively-charged protons and neutral neutrons, surrounded by a large cloud of

light, negatively-charged electrons. Table 2.1 summarizes the properties of these
subatomic particles.
A particular element is defined by its atomic number—the number of protons in
the nucleus (which will equal the number of electrons surrounding the nucleus in a
neutral atom). For example, iron is the element of atomic number 26, meaning that
every iron atom will have 26 protons in its nucleus. Chemists use a one or two-letter
symbol for each element to simplify communication; iron, for example, is given the
symbol Fe, from the old Latin word for iron, ferrum. The sum of the protons plus
neutrons found in the nucleus is called the mass number. For some elements, only
one mass number is found in nature. Fluorine (atomic number 9, mass number 19,
symbol “F”) is an example of such an element. Other elements are found in nature
in more than one mass number. Iron is found as mass number 56 (91.52% abundance
of all iron found in nature), 54 (5.90% abundance), 57 (2.245% abundance), and 58
(0.33% abundance). These different mass numbers of the same element are called
isotopes1 and vary in the number of neutrons found in the nucleus and therefore vary
in their mass as well. Atomic weight refers to the average mass found in nature of
all the atoms of a particular element; the atomic weight of iron is 55.847. For calcu-
lation purposes, these atomic weights are used for the mass of a particular element.
Table 2.2 contains symbols, atomic numbers, and atomic weights for the elements.
In practical terms, only elements 1–83 (hydrogen through bismuth) have use for
“everyday” chemistry, since elements after bismuth are generally radioactive, expen-
sive, inconvenient/unsafe to work with, or all three. Furthermore, the “transuranics”
(beyond uranium) of 93 (neptunium) through 118 (oganesson) are either quite radio-
active and unsafe to handle in normal circumstances or only exist for fractions of a
second—after being synthesized in incredibly complex equipment—before decay-
ing into lighter elements.
Chemical reactivity, and therefore pyrotechnic and explosive behavior, is deter-
mined primarily by the tendency for each element to gain or lose electrons during
a chemical reaction. Calculations of theoretical chemists, with strong support from
experimental studies, suggest that electrons in atoms are found in “orbitals” or

1
The term “isotope” has been commonly and incorrectly used to mean “radioactive material” since
certain isotopes of elements can be significantly radioactive, emitting gamma rays, neutrons, alpha
particles, or beta particles. However, isotopes of elements are not necessarily radioactive, only those
referred to as “radioisotopes” or “radionuclides.”
Another random document with
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 Fig. 2. Union Railway Station, Springfield, Massachusetts
The first roads that improved on the Indian trails were, of course,
made for wagons. The gorge of the Westfield was so rugged that a
hundred years ago it seemed almost impossible to make a good
wagon road through it. There were some people, however, who
thought that it could be done and who determined to do it. Their
courage won, and before long there was a good highway all along
the roaring river. The bowlders were rolled out of the way, the trees
were cut, the roadbed was made, and people could go east and west
in the stages without risk of losing their lives or even of breaking their
bones. This was accomplished soon after 1825, but it did not solve
all the problems of the Massachusetts people, for, as we shall soon
learn fully, the Erie canal was finished in that year, and a long string
of canal boats began to carry produce from the West to New York.
The good people of Boston watched all this going on. Every load
of grain was headed straight eastward as if it were coming to
Massachusetts bay, thence to go by vessel to Europe. But when it
reached the Hudson it was sure to turn off down that river to help
load ships at the piers of New York. And New England had only a
wagon road across the mountains! A wagon road will never draw
trade away from a tidal river, and thus we can understand why a
prominent Massachusetts man, Charles Francis Adams, spoke of
the Hudson as “a river so fatal to Boston.” Boston might have all the
ships she wanted, but if she could not get cargoes for them they
would be of no use. Shipowners, seeing that there was plenty of
western freight in New York, sent their boats there. It was indeed
time that Boston people began to ask themselves what they could
do.
They still had ships, but these were usually “down East”
coasters, and the noble vessels from far eastern ports, laden with
spices and teas, silks, and all the spoils of Europe and Asia, rarely
came to Boston, but brought more and greater loads to New York
and Baltimore, where they could lay in corn and wheat for the return
voyage. Even the Cunards transferred most of their boats and finally
all their mail steamers to New York.
 Fig. 3. The Valley of Deerfield River at Charlemont,
Massachusetts, on the Line of the Boston and Maine
Railroad
The people of Boston first said, “We will build another canal, up
the Hoosick and down the Deerfield valley, and then the canal boats
will keep on to the east.” As states often do, they appointed a
commission to see if the canal could be built, and what it would cost.
But what were they to do about Hoosac mountain, which stood a
thousand feet high, of solid rock, between the Hoosick valley on the
west and the Deerfield valley on the east?
They decided that they would tunnel it for the water way. Rather
strangely they thought it could be done for a little less than a million
dollars. A wise engineer made the survey for the canal, and when he
remarked, “It seems as if the finger of Providence had pointed out
this route from the east to the west,” some one who stood near
replied, “It’s a great pity that the same finger wasn’t thrust through
the mountain.” The plans for the canal were finally given up, and
though many years later such a tunnel was made, it was not for a
canal, nor was the work done for a million dollars.
 Every one was talking now of railways, but few thought that rails
could be laid across the Berkshires. It was even said in a Boston
paper that such a road could never be built to Albany; that it would
cost as much to do it as all Massachusetts would sell for; and that if
it should be finished, everybody with common sense knew it would
be as useless as a railroad from Boston to the moon. We need not
be too hard on this writer, for it was five years later when the De Witt
Clinton train climbed the hill from Albany and carried its handful of
passengers to Schenectady.
One of the friends of the railway scheme was Abner Phelps.
When he was a senior at Williams College, in 1806, he had thought
of it, for he had heard about the tram cars in the English coal
regions. In 1826 he became a member of the legislature of
Massachusetts, and the second day he was there he proposed that
the road should be built.
In time the project went through, but at first it was planned to pull
the cars with horses, and on the down grades to take the horses on
the cars and let them ride. We do not know how it was intended that
the cars should be held back, for it was long before the invention of
air brakes. The line was built to its western end on the Hudson in
1842, and thus Boston, Worcester, Springfield, and Albany were
bound together by iron rails.
There was only a single track and the grades were heavy. The
road brought little trade to Boston, and most of the goods from the
West still went by way of the Hudson to New York. It was, however, a
beginning, and it showed that the mountain wall could be crossed.
The subject of a Hoosac tunnel now came up again. It would
take a long time to tell how the tunnel was made; indeed, it was a
long time in making. It was begun in 1850 or soon afterwards, and
the work went slowly, with many stops and misfortunes, so that the
hole through the mountain was not finished until November 27, 1873.
On that day the last blast was set off, which made the opening from
the east to the west side; and the first regular passenger train ran
through July 8, 1875, fifty years after it had been planned to make a
canal under the mountain.
 In order to help on the work the engineers sunk a shaft a
thousand feet deep from the top of the mountain to the level of the
tunnel, and from the bottom worked east and west. This gave them
four faces, or “headings,” on which to work, instead of two, and
hastened the finishing. The whole cost was about fourteen million
dollars.

Fig. 4. Eastern Portal of the Hoosac Tunnel, Boston and

Maine Railroad
It took great skill to sink the shaft on just the right line, and to
make the parts of the tunnel exactly meet, as the men worked in
from opposite directions. They brought the ends together under the
mountain with a difference of only five sixteenths of an inch! You can
measure this on a finger nail and see how much it is. The
tremendous task was successfully accomplished, and Boston was
no longer shut off from the rest of the country by the mountains.
 Fig. 5. The South Station, Boston
The end of it all is not that Boston has won all the ships away
from New York, but that gradually she has been getting her share.
Now she has great Cunarders, White Star Liners, and the Leyland
boats,—all giant ships sailing for Liverpool,—and many other stately
vessels bound for southern ports or foreign lands. Now you may see
in Boston harbor not a forest of masts but great funnels painted to
show the lines to which the boats belong, and marking a grander
commerce than that which put out for the Indies long years ago; for
to-day Boston is the second American port. The great freight yards
of the railways are close upon the docks, and travelers from the
West may come into either of two great stations, one of which is the
largest railway terminal in the world. In and about Boston are more
than a million people, reaching out with one hand for the riches of
the great land to the west, and with the other passing them over the
seas to the nations on the farther side.
Man has taken a land of dense forests, stony hills, and wild
valleys, and subdued it. It is dotted with cities, crossed by roads, and
is one of the great gateways of North America.
 CHAPTER II
PIONEERS OF THE MOHAWK AND THE
HUDSON

If a stranger from a distant land should come to New York, he

might take an elevated train at the Battery and ride to the upper end
of Harlem. He would then have seen Manhattan island, so named by
the Indians, who but three hundred years ago built their wigwams
there and paddled their canoes in the waters where great ships now
wait for their cargoes. If the visitor should stay for a time, he might
find that Harlem used to be spelled Haarlem, from a famous old town
in Holland. He might walk through Bleecker street, or Cortlandt
street, or see Stuyvesant square, and learn that these hard names
belonged to old Dutch families; and if he studied history, he would
find that the town was once called New Amsterdam and was settled
by Dutchmen from Holland. They named the river on the west of the
island the Great North river, to distinguish it from the Delaware, or
Great South river, and they planned to keep all the land about these
two streams and to call it New Netherland.
Rocks and trees covered most of Manhattan island at that time,
but the Dutch had a small village at its south end, where they built a
fort and set up windmills, which ground the corn and made the place
look like a town in Holland. The Indians did not like the windmills with
their “big teeth biting the corn in pieces,” but they were usually
friendly with the settlers, sometimes sitting before the fireplaces in
the houses and eating supawn, or mush and milk, with their white
friends. Little did the Indian dream what a bargain he offered to the
white man when he consented to sell the whole island for a sum
equal to twenty-four dollars; and the Dutchman, to do him justice,
was equally ignorant.
 All this came about because Henry Hudson with a Dutch vessel,
the Half Moon, had sailed into the harbor in 1609, and had explored
the river for a long distance from its mouth. Hudson was an
Englishman, but with most people he has had to pass for a
Dutchman. He has come down in stories as Hendrick instead of
Henry, no doubt because he commanded a ship belonging to a
Dutch company, and because a Dutch colony was soon planted at
the mouth of the river which he discovered.
Hudson spent a month of early autumn about Manhattan and on
the river which afterwards took his name. Sailing was easy, for the
channel is cut so deep into the land that the tides, which rise and fall
on the ocean border by day and night, push far up the Hudson and
make it like an inland sea. In what we call the Highlands Hudson
found the river narrow, with rocky cliffs rising far above him. Beyond
he saw lowlands covered with trees, and stretching west to the foot
of the Catskill mountains. He went at least as far as the place where
Albany now stands, but there he found the water shallow and turned
his ship about, giving up the idea of reaching the Indies by going that
way. He did not know that a few miles to the west a deep valley lies
open through the mountains, a valley which is now full of busy
people and is more important for travel and trade than a dozen
northwest passages to China would be.
 Fig. 6. Henry Hudson
It was not long before this valley which leads to the west was
found, and by a real Dutchman. Only five years after Hudson’s
voyage Dutch traders built a fort near the spot where Albany now
stands. Shortly afterwards, in 1624, the first settlers came and
founded Fort Orange, which is now Albany. Arent Van Curler came
over from Holland in 1630 and made his home near Fort Orange. He
was an able man and became friendly with the Indians. They called
him “Brother Corlear” and spoke of him as their “good friend.” A few
years ago a diary kept by Van Curler was found in an old Dutch
garret, where it had lain for two hundred and sixty years. It told the
story of a journey that he made in 1634, only four years after he
came to America. Setting out on December 11, he traveled up the
valley of the Mohawk until he reached the home of the Oneida
Indians in central New York. He stayed with them nearly two weeks,
and then returned to Fort Orange, where he arrived on January 19.
This is the earliest record of a white man’s journey through a region
which now contains large towns and is traversed by many railway
trains every day in the year.
No one knows how long there had been Indians and Indian trails
in the Mohawk valley. These trails Van Curler followed, often coming
upon some of the red men themselves, and visiting them in a friendly
way. They, as well as the white settlers who followed them, chose
the flat, rich lands along the river, for here it was easy to beat a path,
and with their bark canoes they could travel and fish. The Indians
entertained Van Curler with baked pumpkins, turkey, bear meat, and
venison. As the turkey is an American bird, we may be sure that it
was new to the Dutch explorer.
These Indians, with whom Van Curler and all the New York
colonists had much to do, were of several tribes,—the Mohawks,
Oneidas, Onondagas, Cayugas, and Senecas. All together they
were known as the Iroquois (ĭr-ṓ-kwoi´), or Iroquois Nation, a kind of
confederation which met in council and went forth together to war.
They called their five-fold league The Long House, from the style of
dwelling which was common among them,—a long house in which
as many as twenty families sometimes lived. The Iroquois built
villages, cultivated plots of land, and sometimes planted apple
orchards. They were often eloquent orators and always fierce
fighters. Among the surrounding tribes they were greatly feared.
They sailed on lake Ontario and lake Erie in their birch-bark canoes,
and they followed the trails far eastward down the Mohawk valley.
Before the white men came these fierce warriors occasionally
invaded New England, to the terror of the weaker tribes. Sometimes
they followed up their conquests by exacting a tribute of wampum.
After Fort Orange was founded they went there with their packs of
beaver skins and other furs to trade for clothes and trinkets.
In fact the white man’s principal interest for many years was to
barter for furs. The Dutch, and soon afterwards the English, bid for
the trade from their settlements on the Hudson, and the French did
the same from their forts on the St. Lawrence and the Great Lakes.
Thus there was much letter writing and much fighting among the
colonists, while each side tried to make friends of the Indians and get
the whole of the fur trade. The result was that either in war or in
trade the white men and the savages were always going up and
down the Mohawk valley, which thus was a well-traveled path long
before there were turnpike roads, canals, or steam cars.
When Van Curler made his journey into the Indian country, he
did not reach the Mohawk river at once on leaving Fort Orange, but
traveled for about sixteen miles across a sandy and half-barren
stretch of scrubby pine woods. He came down to the river where its
rich bottom lands spread out widely and where several large islands
are inclosed by parts of the stream. South and east of these flats are
the sand barrens, and on the west are high hills through which, by a
deep, narrow gap, the Mohawk flows. The Indians called this place
“Schonowe,” or “gateway.” It was well named, for entering by this
gate one can go to the foot of the Rocky mountains without climbing
any heights.
A few years before his death Van Curler led a small band of
colonists from Fort Orange, bought the “great flats” from the Mohawk
Indians, and founded a town, calling it Schenectady, which is the old
Indian name changed in its spelling. No easy time did these settlers
have, for theirs was for many years the frontier town and they never
knew when hostile savages might come down upon them to burn
their houses and take their scalps. In 1690, twenty-eight years after
the town was founded, a company of French and Indians from
Montreal surprised Schenectady in the night, burned most of the
houses, and killed about sixty of the people, taking others captive.
But Dutchmen rarely give up an undertaking, and they soon rebuilt
their town. It was an important place, for here was the end of the
“carry” over the pine barrens from the Hudson, and here began the
navigation of the river, which for a hundred years was the best
means of carrying supplies up the valley and into central New York.
The traveler of to-day on the New York Central Railway sees on
Van Curler’s “great flats” the flourishing city of Schenectady, with its
shops and houses, its college, and its vast factories for the
manufacture of locomotives and electrical supplies.
 Fig. 7. Sir William
Johnson
See Fort Johnson, Fig. 9

It is true that the Dutch pioneers played an important part in the

early history of the state and are still widely represented by their
descendants in the Mohawk valley, but the leading spirit of colonial
days on the river was a native of Ireland who came when a young
man to manage his uncle’s estates in America. This was in 1738,
nearly fifty years after the Schenectady massacre. The young man,
who was in the confidence of the governor of New York and of the
king as well, is known to all readers of American history as Sir
William Johnson.
He built a fine stone mansion a short distance west of the
present city of Amsterdam and lived there many years. He also
founded Johnstown, a few miles to the north, now a thriving little city.
He dealt honestly with the Indians, when many tried to get their lands
by fraud, and he served as a high officer in the French and Indian
wars.
As the Dutch settled the lower Mohawk valley, so the upper parts
were taken up and the forests cleared by Yankees from New
England. One of these was Hugh White, a sturdy man with several
grown children. He left Middletown, Connecticut, in 1784, and came
by water to Albany, sending one of his sons overland to drive two
pair of oxen. Father and son met in Albany and went together across
the sands to Schenectady, where they bought a boat to take some of
the goods up the river. Four miles west of where Utica now stands
they stopped, cut a few trees, and built a hut to shelter them until
they could raise crops and have a better home. Thus the ancient
village of Whitesboro was founded. White was one of many hardy
and brave men who settled in central New York at that time, and they
doubtless thought that they had gone a long way “out West.”
Certainly their journey took more time than the emigrant would now
need to reach California or Oregon.
To cut the trees, build cabins, guard against the savages, and
get enough to eat and wear gave the settlers plenty to do. Only the
simplest ways of living were possible. Until a grist mill was built they
often used samp mortars, such as the Indians made. They took a
section of white ash log three feet long, and putting coals of fire on
one end, kept them burning with a hand bellows until the hole was
deep enough to hold the corn, which was then pounded for their
meals of hominy. By and by a mill was built, and here settlers often
came from a distance of many miles, sometimes carrying their grists
on their backs. A dozen years after White came, General William
Floyd set up another mill in the northern part of what is now Oneida
county. He was one of the signers of the Declaration of
Independence.
One settler cleared several acres and planted corn with pumpkin
seeds sprinkled in. The pigeons pulled up all the corn, but hundreds
of great pumpkins grew and ripened. Since the crop was hardly
enough, however, for either men or beasts, the latter had to be fed
the next winter on the small top boughs of the elm, maple, and
basswood.
Much use was made of the river, for the only roads were Indian
paths through the woods on the river flats. People and freight were
carried in long, light boats suited to river traffic and known as
bateaux (bȧ-tō̟ s´). These could be propelled with oars, but poles
were necessary going upstream against a stiff current. It was
impossible to go up the Mohawk from the Hudson above Albany, on
account of the great falls at Cohoes; hence the long carry to
Schenectady. From that place, by hard work, the boatmen could
make their way up to Little Falls, where the water descends forty feet
in roaring rapids. Here the loads and the bateaux had to be carried
along the banks to the still water above, where, with many windings
and doublings on their course, the voyagers could reach the Oneida
Carrying Place, or Fort Stanwix. There they unloaded again, and for
a mile or more tramped across low ground to Wood creek, a little
stream flowing into Oneida lake, and thence into Oswego river and
lake Ontario. The city of Rome stands exactly on the road followed
by the “carry.” This was an important place, and was called by the
Dutch Trow Plat, while to the Indians it was De-o-wain-sta, “the place
where canoes are carried across.” Several forts were built there, of
which the most famous was Fort Stanwix. We should think Wood
creek a difficult bit of navigation. It was a small stream, very crooked,
and often interrupted by fallen trees. In times of low water the boats
were dragged up and even down the creek by horses walking in the
water.

Fig. 8. Genesee Street, Utica

Part of the old Genesee road
 The first merchant of old Fort Schuyler (Utica) was John Post,
who had served his country well through the Revolution. In 1790 he
brought hither his wife, three little children, and a carpenter from
Schenectady, after a voyage of about nine days up the river. Near
the long-used fording place he built a store, at the foot of what is now
Genesee street. Here he supplied the simple needs of the few
families in the new hamlet, and bought furs and ginseng of the
Indians, giving in exchange paint, powder, shot, cloth, beads,
mirrors, and, it must be added, rum also. Thus the fact that the river
was shallow at this point and could be passed without a bridge or a
boat led to the founding of the city of Utica.
The first regular mail reached the settlement in 1793, the post
rider being allowed twenty-eight hours to come up from Canajoharie,
a distance of about forty miles, now traversed by many trains in
much less than an hour. On one occasion the Fort Schuyler
settlement received six letters in one mail. The people would hardly
believe this astonishing fact until John Post, who had been made
postmaster, assured them that it was true. Post established stages
and lines of boats to Schenectady, and soon had a large business,
for people were pouring into western New York to settle upon its
fertile lands.
All the boats did not go down to Oswego and lake Ontario. Some
turned and entered the Seneca river, following its slow and winding
waters to the country now lying between Syracuse and Rochester.
But these boats were not equal to the traffic, for the new farms were
producing grain to be transported, and the people needed many
articles from the older towns on the Atlantic coast. Hence about a
dozen years after Hugh White built his first cabin by the river, the
state legislature took up the question of transportation and built a
great road, a hundred miles long, from Fort Schuyler, or the future
Utica, to Geneva, at the foot of Seneca lake.
The road as laid out was six rods wide. It was improved for a
width of four rods by the use of gravel and logs where the ground
was soft and swampy, as much of it was in those days, being flat and
shaded by trees. Over the famous Genesee road, as it was called,
thousands of people went not only to the rich valley of the Genesee
in western New York but also on to Ohio, and even to the prairies of
the Mississippi river. Genesee street in Utica and Genesee street in
Syracuse are parts of this road. The historian tells of it as a triumph,
for it was an Indian path in June, and before September was over a
stage had started at Fort Schuyler, and on the afternoon of the third
day had deposited its four passengers at the hotel in Geneva. After
this wagons and stages began to run frequently between Albany and
Geneva. A wagon could carry fourteen barrels of flour eastward, and
in about a month could return to Geneva from Albany with a load of
needed supplies. In five weeks, one winter, five hundred and seventy
sleighs carrying families passed through Geneva to lands farther
west.
Geneva was quite a metropolis in those days, when there was
nothing but woods where Syracuse and Rochester now are. Regular
markets were held there, for there were fine farms and orchards
about the beautiful shores of Seneca lake. It is recorded as
remarkable that one settler had “dressed up” an old Indian orchard
and made “one hundred barrels of cyder.”
We might think that the founders of the city of Rochester would
have come in by the Genesee road, but they did not. Far to the
south, at Hagerstown in Maryland, a country already old, lived
Colonel Rochester. He heard of the Genesee lands and at last
bought, with his partners, a hundred acres by the falls, where the city
now stands. When the little family procession passed down the
street and entered upon the long journey up the Susquehanna valley
to western New York, Rochester’s friends in Hagerstown wept to see
him go. They thought that he had thrown his money away in buying
swamp lands where only mosquitoes, rattlesnakes, and bears could
live, but he saw farther than they did. If he had been unwilling to take
any risk, he would never have laid out the first streets of the
prosperous city which now bears his name.
 Fig. 9. Old Fort Johnson, Amsterdam, New York
Built by Sir William Johnson, 1742
Syracuse, like Utica and Rochester, had its own way of
beginning. We can truly say that at first salt made the city. The beds
of salt are not directly under Syracuse, but are in the hills not far
away. The water from the rains and springs dissolves some of this
salt, and as it flows down it fills the gravels in and around the town.
While all was yet forest the Indian women had made salt from the
brine which oozed up in the springs. So long ago as 1770, five years
before the Revolution, the Delaware Indians went after Onondaga
salt, and a little of it was now and then brought down to Albany.
Sometimes it was sold far down the St. Lawrence in Quebec.
 New York
New York, Lake Erie and Western Railroad —————
Delaware, Lackawanna and Western Railroad .....................
New York Central and Hudson River Railroad ---------
New York, Ontario and Western Railroad -·-·-·-·-·-·-·-
Delaware and Hudson Railroad +-+-+-+-+-+
Erie Canal (old location) =========

The pioneers first made salt there in 1788. This was several
years before the Genesee road was cut through the woods. One of
these men, a Mr. Danforth, whose name a suburb of Syracuse now
bears, used to put his coat on his head for a cushion and on that
carry out a large kettle to the springs. He would put a pole across
crotched sticks, hang up the kettle, and go to work to make salt.
When he had made enough for the time he would hide his kettle in
the bushes and bring home his salt. By and by so many hundreds of
bushels were made by the settlers that the government of the state
framed laws to regulate the making and selling of the salt, and as
time went on a town arose and grew into a city. Many years later
rock salt was found deep down under the surface farther west, and
since that discovery the business of Syracuse has become more and
more varied in character.
The history of the state of New York shows well how the New
World was settled along the whole Atlantic coast. The white men
from Europe found first Manhattan island and the harbor. Then they
followed the lead of a river and made a settlement that was to be
Albany. Still they let a river guide them, this time the Mohawk, and it
led them westward. They pushed their boats up the stream, and on
land they widened the trails of the red men. Near its head the
Mohawk valley led out into the wide, rich plains south and east of
lake Ontario. Soon there were so many people that a good road
became necessary. When the good road was made it brought more
people, and thus the foundations of the Empire State were laid.
 CHAPTER III
ORISKANY, A BATTLE OF THE REVOLUTION

About halfway between old Fort Schuyler, or Utica, and Fort

Stanwix, which is now Rome, is the village of Oriskany. A mile or two
west of this small town, in a field south of the Mohawk river, stands a
monument raised in memory of a fierce battle fought on that slope in
the year following the Declaration of Independence. On the pedestal
are four tablets in bronze, one of which shows a wounded general
sitting on the ground in the woods, with his hand raised, giving
orders to his men. The time was 1777, the strife was the battle of
Oriskany, and the brave and suffering general was Nicholas
Herkimer.
On another of the tablets is this inscription:
Here was fought
The battle of Oriskany
On the 6th day of August, 1777.
Here British invasion was checked and thwarted.
Here General Nicholas Herkimer,
Intrepid leader of the American forces,
Though mortally wounded kept his command of the fight
Till the enemy had fled.
The life blood of more than
Two hundred patriot heroes
Made this battle ground
Sacred forever.
After the battle Herkimer was carried down the valley to his
home, where a few days later he died. On the field he had calmly
lighted his pipe and smoked it as he gave his orders, refusing to be