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Library of Congress Cataloging in Publication Data PREFACE

Conkling, John A., [date]

Chemistry of pyrotechnics.

Includes bibliographies and index.

1. Fireworks. I. Title.

TP300.C66 1985

6621 . 1

85-7017

ISBN 0-8247-7443-4

Everyone has observed chemical reactions involving pyrotechnic mixtures. Beautiful 4th of July fireworks, highway distress signals, Warning: Formulas in this book relate to mixtures, some or all solid fuel boosters for the Space Shuttle, and the black powder used of which may be highly volatile and could react violently if ignited by muzzle-loading rifle enthusiasts all have a common technical back-by heat, spark, or friction. High-energy mixtures should never ground.

be prepared or handled by anyone untrained in proper safety pre-The chemical principles underlying these high-energy materials cautions. All work in connection with pyrotechnics and explosives have been somewhat neglected in the twentieth century by academic should be done only by experienced personnel and only with appro-and industrial researchers. Most of the recent work has been goal-priate environmental safeguards. The publisher and the author oriented rather than fundamental in nature (e.g. , produce a deeper disclaim all responsibility for injury or damage resulting from use green flame). Many of the significant results are found in military of any formula or mixture described in this book ; each user assumes reports, and chemical fundamentals must be gleaned from many pages all liability resulting from such usage.

of test results.

ing World War II, and they are presently fast approaching (if not already past) retirement age. This is most unfortunate for future Neither this book nor any part may be reproduced or transmitted in researchers. Newcomers have a difficult time acquiring the skills and any form or by any means, electronic or mechanical, including photo-knowledge needed to begin productive experiments. A background copying, microfilming, and recording, or by any information storage in chemistry is helpful, but much of today's modern chemistry cur-and retrieval system, without permission in writing from the pub-riculum will never be used by someone working in pyrotechnics and lisher.

explosives. Further, the critical education in how to safely mix, MARCEL DEKKER, INC.

handle, and store high-energy materials is not covered at all in to-270 Madison Avenue, New York, New York 10016

day's schools and must be acquired in "on-the-job" training.

This book is an attempt to provide an introduction to the basic Current printing (last digit)

principles of high-energy chemistry to newcomers and to serve as a 10 9 8 7 6

review for experienced personnel. It can by no means substitute PRINTED IN THE UNITED STATES OF AMERICA

for the essential "hands on" experience and training necessary to iii

Preface

safely work in the field, but I hope that it will be a helpful compan-1

ion. An attempt has been made to keep chemical theory simple and directly applicable to pyrotechnics and explosives. The level approaches that of an introductory college course, and study of this text may prepare persons to attend professional meetings and seminars dealing with high-energy materials and enable them to intelli-gently follow the material being presented. In particular, the International Pyrotechnic Seminars, hosted biannually by the Illinois CONTENTS

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 information 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 encouragement and their willingness to rec-Preface

ill

ognize 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 CHAPTER 1 INTRODUCTION

my thanks to many colleagues in the field of pyrotechnics who have Brief History

provided me with data as well as encouragement, and to my 1983 and References

1984 Summer Chemistry Seminar groups at Washington College for their review of draft versions of this book. I also appreciate the CHAPTER 2 BASIC CHEMICAL PRINCIPLES

support and encouragement given to me by my wife and children as Atoms and Molecules

I concentrated on this effort.

The Mole Concept

Finally, I must acknowledge the many years of friendship and Electron Transfer Reactions

collaboration that I enjoyed with Dr. Joseph H. McLain, former Thermodynamics

Chemistry Department Chairman and subsequently President of Rates of Chemical Reactions

Washington College. It was his enthusiasm and encouragement that Energy-Rich Bonds

dragged me away from the norbornyl cation and physical organic States of Matter

chemistry into the fascinating realm of pyrotechnics and explosives.

Acids and Bases

The field of high-energy chemistry lost an important leader when Instrumental Analysis

Dr. McLain passed away in 1981.

Light Emission

References

John A. Conkling

CHAPTER 3 COMPONENTS OF HIGH-ENERGY

MIXTURES

Introduction

Oxidizing Agents

Fuels

Binders

Retardants

References

Contents

CHAPTER 4 PYROTECHNIC PRINCIPLES

Introduction

Requirements for a Good High-Energy Mixture

Preparation of High-Energy Mixtures

References

CHEMISTRY OF

CHAPTER 5 IGNITION AND PROPAGATION

Ignition Principles

Sensitivity

108

PYROTECHNICS

Propagation of Burning

111

References

123

CHAPTER 6 HEAT AND DELAY COMPOSITIONS

125

Heat Production

125

Delay Compositions

128

Ignition Compositions and First Fires

133

Thermite Mixtures

134

Propellants

136

References

140

CHAPTER 7 COLOR AND LIGHT PRODUCTION

143

White Light Compositions

143

Sparks

147

Flitter and Glitter

149

Color

150

References

165

CHAPTER 8 SMOKE AND SOUND

167

Smoke Production

167

Colored Smoke Mixtures

169

White Smoke Production

172

Noise

176

References

i79

APPENDIXES

181

Appendix A : Obtaining Pyrotechnic Literature 181

Appendix B : Mixing Test Quantities of Pyrotechnic Compositions

182

I ndex

185

Fireworks burst in the sky over the Washington Monument to celebrate Independence Day. Such fireworks combine all of the effects that can be created using pyrotechnic mixtures. A fuse made with black powder provides a time delay between lighting and launching.

A propellant charge--also black powder-lifts each fireworks cannis-ter hundreds of feet into the air. There, a "bursting charge" ruptures the casing while igniting numerous small "stars"--pellets of composition that burn with vividly-colored flames. (Zambelli Internationale)

I NTRODUCTION

This book is an introduction to the basic principles and theory of pyrotechnics. Much of the material is also applicable to the closely-related areas of propellants and explosives. The term "high-energy chemistry" will be used to refer to all of these fields. Explosives rapidly release large amounts of energy, and engineers take advantage of this energy and the associated shock and pressure to do work. Pyrotechnic mixtures react more slowly, producing light, color, smoke, heat, noise, and motion.

The chemical reactions involved are of the electron-transfer, or oxidation-reduction, type. The compounds and mixtures to be studied are almost always solids and are designed to function in the absence of external oxygen. The reaction rates to be dealt with range along a continuum from very slow burning to "instantaneous" detonations with rates greater than a kilometer per second (Table 1. 1).

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 serve as the first example of a "high-energy material" due to its historical significance. Black powder is an intimate mixture of potassium nitrate (75% by weight), charcoal (15%), and sulfur (10%). A reactive black powder is no simple material to prepare. If one merely mixes the three components briefly, a powder 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, readily I

Introduction

Chemistry of Pyrotechnics

black powder as a propellant and delay mixture in many applica-TABLE 1. 1 Classes of "High-Energy" Reactions tions, there is still a sizeable demand for black powder in both the military and civilian pyrotechnic industries. How many black Approximate

powder factories are operating in the United States today? Ex-Class

reaction velocity

Example

actly one. The remainder have been destroyed by explosions or closed because of the probability of one occurring. In spite of Burning

Millimeters/second

Delay mixtures, colored

a demand for the product, manufacturers are reluctant to engage smoke composition

in the production of the material because of the history of prob-Deflagration

Meters /second

Rocket propellants, con-

lems with accidental ignition during the manufacturing process.

fined black powder

Why is black powder so sensitive to ignition? What can the chemist do to minimize the hazard? Can one alter the performance of Detonation

> 1 Kilometer /second

Dynamite, TNT

black powder by varying the ingredients and their percentages, using theory as the approach rather than trial-and-error? It is this type of problem and its analysis that I hope can be addressed a bit more scientifically with an understanding of the fundamental concepts presented in this book. If one accident can be prevented ignite and burn rapidly. Particle size, purity of starting materias a consequence of someone's better insight into the chemical nature of high-energy materials, achieved through study of this als, mixing time, and a variety of other factors are all critical in producing high-performance black powder. Also, deviations from book, then the effort that went into its preparation was worth-the 75/15/10 ratio of ingredients will lead to substantial changes while.

in performance. Much of the history of modern Europe is related to the availability of high-quality black powder for use in rifles and cannons. A good powder-maker was essential to military suc-BRIEF HISTORY

cess, although he usually received far less recognition and dec-oration than the generals who relied upon his product.

The use of chemicals to produce heat, light, smoke, noise, and The burning behavior of black powder illustrates how a pyro-motion has existed for several thousand years, originating most technic mixture can vary in performance depending on the condi-likely in China or India. India has been cited as a particularly good possibility due to the natural deposits of saltpeter (potas-tions of its use. A small pile of loose black powder can be readily ignited by the flame from a match, producing an orange flash and sium nitrate, KNO 3) found there [1].

a puff of smoke, but almost no noise. The same powder, sealed Much of the early use of chemical energy involved military ap-in a paper tube but still in loose condition, will explode upon ig-plications. "Greek fire," first reported in the 7th century A.D. , nition, rupturing the container with an audible noise. Black pow-was probably a blend of sulfur, organic fuels, and saltpeter that der spread in a thin trail will quickly burn along the trail, a generated flames and dense fumes when ignited. It was used in property used in making fuses. Finally, if the powder is com-a variety of incendiary ways in both sea and land battles and pressed in a tube, one end is left open, and that end is then added a new dimension to military science [2].

constricted to partially confine the hot gases produced when the At some early time, prior to 1000 A.D. , an observant scientist powder is ignited, a rocket-type device is produced. This varied recognized the unique properties of a blend of potassium nitrate, behavior is quite typical of pyrotechnic mixtures and illustrates sulfur, and charcoal; and black powder was developed as the first why one must be quite specific in giving instructions for pre-

"modern" high-energy composition. A formula quite similar to the paring and using the materials discussed in this book.

one used today was reported by Marcus Graecus ("Mark the Greek") Why should someone working in pyrotechnics and related areas in an 8th century work "Book of Fires for Burning the Enemy"

bother to study the basic chemistry involved? Throughout the

[ 2]. Greek fire and rocket-type devices were also discussed in 400-year "modern" history of the United States many black pow-these writings.

der factories have been constructed and put into operation. Al-The Chinese were involved in pyrotechnics at an early date though smokeless powder and other new materials have replaced and had developed rockets by the 10th century [1]. Fireworks

Chemistry of Pyrotechnics

Introduction

were available in China around 1200 A.D. , when a Spring Festi-then be produced. Strontium, barium, and copper compounds val reportedly used over 100 pyrotechnic sets, with accompany-capable of producing vivid red, green, and blue flames also being music, blazing candle lights, and merriment. The cost of came commercially available during the 19th century, and mod-such a display was placed at several thousand Bangs of silver ern pyrotechnic technology really took off.

(one Hang = 31. 2 grams) [ 3] . Chinese firecrackers became a Simultaneously, the discovery of nitroglycerine in 1846 by popular item in the United States when trade was begun in the Sobrero in Italy, and Nobel's work with dynamite, led to the de-1800's. Chinese fireworks remain popular in the United States velopment of a new generation of true high explosives that were today, accounting for well over half of the annual sales in this far superior to black powder for many blasting and explosives country. The Japanese also produce beautiful fireworks, but, applications. The development of modern smokeless powder -

curiously, they do not appear to have developed the necessary using nitrocellulose and nitroglycerine - led to the demise of technology until fireworks were brought to Japan around 1600

black powder as the main propellant for guns of all types and A.D. by an English visitor [4]. Many of the advances in fire-sizes.

works technology over the past several centuries have come Although black powder has been replaced in most of its for-from these two Asian nations.

mer uses by newer, better materials, it is important to recog-The noted English scientist Roger Bacon was quite familiar nize the important role it has played in modern civilization.

with potassium nitrate/charcoal/sulfur mixtures in the 13th cen-Tenney Davis, addressing this issue in his classic book on the tury, and writings attributed to him give a formula for preparing chemistry of explosives, wrote "The discovery that a mixture of

"thunder and lightning" composition [5]. The use of black pow-potassium nitrate, charcoal, and sulfur is capable of doing useder as a propellant for cannons was widespread in Europe by the ful work is one of the most important chemical discoveries or in-14th century.

ventions of all time ... the discovery of the controllable force of Good-quality black powder was being produced in Russia in gunpowder, which made huge engineering achievements possible, the 15th century in large amounts, and Ivan the Terrible report-gave access to coal and to minerals within the earth, and brought edly had 200 cannons in his army in 1563 [6]. Fireworks were on directly the age of iron and steel and with it the era of ma-being used for celebrations and entertainment in Russia in the chines and of rapid transportation and communication" [5].

17th century, with Peter the First among the most enthusiastic Explosives are widely used today throughout the world for supporters of this artistic use of pyrotechnic materials.

mining, excavation, demolition, and military purposes. Pyro-By the 16th century, black powder had been extensively stud-technics are also widely used by the military for signalling and ied in many European countries, and a published formula dating training. Civilian applications of pyrotechnics are many and to Bruxelles in 1560 gave a 75.0/15.62/9.38 ratio of saltpeter/

varied, ranging from the common match to highway warning charcoal /sulfur that is virtually the same as the mixture used flares to the ever-popular fireworks.

today [51!

The fireworks industry remains perhaps the most visible ex-The use of pyrotechnic mixtures for military purposes in rifles, ample of pyrotechnics, and also remains a major user of tradi-rockets, and cannons developed simultaneously with the civilian tional black powder. This industry provides the pyrotechnician applications such as fireworks. Progress in both areas followed with the opportunity to fully display his skill at producing col-advances in modern chemistry, as new compounds were isolated ors and other brilliant visual effects.

and synthesized and became available to the pyrotechnician.

Fireworks form a unique part of the cultural heritage of many Berthollet's discovery of potassium chlorate in the 1780's resulted countries [7]. In the United States, fireworks have traditionally in the ability to produce brilliant flame colors using pyrotechnic been associated with Independence Day - the 4th of July. In compositions, and color was added to the effects of sparks, noise, England, large quantities are set off in commemoration of Guy and motion previously available using potassium nitrate-based Fawkes Day (November 5th), while the French use fireworks compositions. Chlorate -containing color-producing formulas were extensively around Bastille Day (July 14th). In Germany, the known by the 1830's in some pyrotechnicians' arsenals.

use of fireworks by the public is limited to one hour per year -

The harnessing of electricity led to the manufacturing of mag-from midnight to 1 a.m. on January 1st, but it is reported to be nesium and aluminum metals by electrolysis in the latter part of quite a celebration. Much of the Chinese culture is associated the 19th century, and bright white sparks and white light could with the use of firecrackers to celebrate New Year's and other

Chemistry of Pyrotechnics

important occasions, and this custom has carried over to Chinese communities throughout the world. The brilliant colors and booming noises of fireworks have a universal appeal to our basic senses.

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.

REFERENCES

U.S. Army Material Command, Engineering Design Handbook, Military Pyrotechnic Series, Part One, "Theory and Application," Washington, D.C., 1967 (AMC Pamphlet 706-185).

J. R. Partington, A History of Greek Fire and Gunpowder, W. Heffer and Sons Ltd. , Cambridge, Eng. , 1960.

Ding Jing, "Pyrotechnics in China," presented at the 7th International Pyrotechnics Seminar, Vail, Colorado, July, 1980.

T. Shimizu, Fireworks - The Art, Science and Technique,

pub. by T. Shimizu, distrib. by Maruzen Co., Ltd., Tokyo, 1981.

T. L. Davis, The Chemistry of Powder and Explosives, John Wiley & Sons, Inc., New York, 1941.

A. A. Shidlovskiy, Principles of Pyrotechnics, 3rd Edition, Moscow, 1964. (Translated as Report FTD-HC-23-1704-74

by Foreign Technology Division, Wright-Patterson Air Force Base, Ohio, 1974.)

G. Plimpton, Fireworks:

A History and Celebration, Double-

day, New York, 1984.

A grain of commercially-produced black powder, magnified 80 times.

Extensive mixing and grinding of moist composition produces a homogeneous mixture of high reactivity. A mixture of the same three components-potassium nitrate, sulfur, and charcoal-that is prepared by briefly stirring the materials together will be much less reactive.

(J. H. McLain files)

2BASIC CHEMICAL PRINCIPLES

ATOMS AND MOLECULES

To understand the chemical nature of pyrotechnics, one must begin at the atomic level. Two hundred years of experiments and 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 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 is given the symbol Fe, from the old Latin word for iron, ferrum. The sum of the protons plus neutrons found in a nucleus is called the mass number. For some elements only one mass number is found in nature. Fluorine (atomic number 9, mass number 19) 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%), 54 (5.90%), 57 (2.245%), and 58 (0.33%) . These different mass numbers of the same element are called isotopes, and vary in the number of neutrons found in the nucleus. 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 calculation purposes, these 7

Chemistry of Pyrotechnics

Basic Chemical Principles

TABLE 2.1 Properties of the Subatomic Particles TABLE 2.2 Symbols, Atomic Weights, and Atomic Numbers of the Elements

Particle

Location

Charge

Mass, amusa

Mass, grams

-24

Atomic

Atomic weight,

Proton

In nucleus

1.007

1.673 X 10

Element

Symbol

-24

number

amusa

Neutron In nucleus

1.009

1.675 X 10

-28

Actinium

Electron

Outside nucleus

-1

0.00549

9.11 X 10

Aluminum

26.9815

Americium

a amu = atomic mass unit, where 1 amu = 1.66 X 10 -24 gram.

Antimony

121.75

Argon

39.948

Arsenic

74.9216

Astatine

Barium

atomic weights are used for the mass of a particular element.

137.34

Table 2.2 contains symbols, atomic numbers, and atomic weights Berkelium

Beryllium

for the elements.

9.0122

Chemical reactivity, and therefore pyrotechnic and explosive Bismuth

208.980

Boron

behavior, is determined primarily by the tendency for each eleB

10.811

Bromine

ment to gain or lose electrons during a chemical reaction. Cal-35

79.909

Cadmium

culations by theoretical chemists, with strong support from ex-48

112.40

Calcium

perimental studies, suggest that electrons in atoms are found in 20

40.08

Californium

"orbitals," or regions in space where they possess the lowest possible energy - close to the nucleus but away from other neg-Carbon

12.01115

Cerium

140.12

atively-charged electrons.

As electrons are placed into an atom,

Cesium

energy levels close to the positive nucleus are occupied first, Cs

132.905

Chlorine

and the higher energy levels are then successively populated.

35.453

Chromium

Extra stability appears to be associated with completely filled 24

51.996

Cobalt

levels, termed "shells." Elements with completely filled shells 58.9332

Copper

include helium (atomic number 2), neon (atomic number 10), 63.54

Curium

argon (atomic number 18), and krypton (atomic number 36).

Dysprosium

162.50

These elements all belong to a group called the "inert gases,"

Einsteinium

and their virtual lack of any chemical reactivity provides sup-Es

Erbium

port for the theory of filled-shell stability.

167.26

Europium

Other elements show varying tendencies to obtain a filled 151.96

Fermium

100

shell by the sharing of electrons with other atoms, or by the Fluorine

actual gain or loss of electrons to form charged species, called 18.9984

Francium

ions.

For example, sodium (symbol Na, atomic number 11) Gadolinium

readily loses one electron to form the sodium ion, Na+, with 10

157.25

Gallium

69.72

electrons.

By losing one electron, sodium has acquired the same Germanium

number of electrons as the inert gas neon, and it has become a 32

72.59

Gold

very stable chemical species. Fluorine (symbol F, atomic num-196.967

Hafnium

ber 9) readily acquires one additional electron to become the Hf

178.49

Helium

fluoride ion, F - .

This is another 10-electron species and is

4.0026

VI J

Chemistry of Pyrotechnics

Basic Chemical Principles

TABLE 2.2 (continued)

Atomic

Atomic weight,

Atomic

Atomic weight,

Element

Symbol

number

amusa

Element

Symbol

number

amus a

Holmium

164.930

Rubidium

85.47

Hydrogen

1.00797

Ruthenium

101.07

Indium

114.82

Samarium

150.35

Iodine

126.9044

Scandium

44.956

Iridium

192.2

Selenium

78.96

Iron

55.847

Silicon

28.086

Krypton

83.80

Silver

A g

4 7

107.870

Lanthanum

138. 91

Sodium

22.9898

Lead

207.19

Strontium

87.62

Lithium

6.939

Sulfur

32.064

Lutetium

174. 97

Tantalum

180.948

Magnesium

24.312

Technetium

Manganese

54.9380

Tellurium

127.60

Mendelevium

101

Terbium

158.924

Mercury

200.59

Thallium

204.37

Molybdenum

95.94

Thorium

T h

232.038

Neodymium

144.24

Thulium

6 9

168.934

Neon

20.183

Tin

118.69

Neptunium

Titanium

47.90

Nickel

58.71

Tungsten

183.85

Niobium

92.906

Uranium

238.03

Nitrogen

14.0067

Vanadium

2 3

50.942

Nobelium

102

Xenon

131.30

Osmium

190.2

Ytterbium

173.04

Oxygen

15.9994

Yttrium

88.905

Palladium

106.4

Zinc

65.37

Phosphorus

30.9738

Zirconium

91.22

Platinum

195.09

-24

Plutonium

amu = atomic mass unit, where 1 amu = 1.66 X 10

gram.

Polonium

Potassium

39.102

Praseodymium

140.907

Promethium

quite stable.

Other elements display similar tendencies to gain Protactinium

or lose electrons to acquire "inert gas" electron configurations Radium

by becoming positive or negative ions. Many chemical species found in nature are ionic compounds. These are crystalline Radon

Rhenium

186.2

solids composed of interpenetrating lattices of positive and neg-Rhodium

102.905

ative ions held together by electrostatic attraction between these Oppositely-charged particles.

Table salt, or sodium chloride, is

Chemistry of Pyrotechnics

Basic Chemical Principles

an ionic compound consisting of sodium and chloride ions, Na+

TABLE 2.3 Electronegativity Values for Some

and Cl- , and one uses the formula NaCl to represent the one-to-Common Elements

one ionic ratio. The attractive forces holding the solid together are called ionic bonds.

Pauling electronegativity

Hence, if one brings together a good electron donor (such as Element

valuea

a sodium atom) and a good electron acceptor (such as a fluorine atom), one might expect a chemical reaction to occur. Electrons Fluorine, F

4.0

are transferred and an ionic compound (sodium fluoride, NaF) Oxygen, 0

3.5

is produced.

Nitrogen, N

3.0

Chlorine, Cl

3.0

Na + F - Na+F- (sodium fluoride)

Bromine, Br

2.8

A three-dimensional solid lattice of sodium and fluoride ions Carbon, C

2.5

is created, where each sodium ion is surrounded by fluoride Sulfur, S

2.5

ions, and each fluoride ion in turn is surrounded by sodium Iodine, I

2.5

ions. Another very important aspect of such a reaction is the Phosphorus, P

2.1

fact that energy is released as the product is formed. This re-Hydrogen, H

2.1

lease of energy associated with product formation is most important in the consideration of the chemistry of pyrotechnics.

aSource: L. Pauling, The Nature of the Chemical In addition to forming ions by electron transfer, atoms may Bond, Cornell University Press, Ithaca, NY, 1960.

share electrons with other atoms as a means of acquiring filled shells (and their associated stability). The simplest illustration of this is the combination of two hydrogen atoms (symbol H, atomic number 1) to form a hydrogen molecule.

H + Cl -> H-Cl (hydrogen chloride)

H + H -} H-H (H

By this combination, both atoms now have "filled shell" elec-2 , a molecule)

tronic configurations and a hydrogen chloride molecule is formed.

The sharing of electrons between two atoms is called a covalent The sharing here is not exactly equal, however, for chlorine is bond. Such bonds owe their stability to the interaction of the a stronger electron attractor than hydrogen. The chlorine end shared electrons with both positive nuclei. The nuclei will be of the molecule is slightly electron rich; the hydrogen end is separated by a certain distance -- termed the bond distance -

electron deficient. This behavior can be noted using the Greek that maximizes the nuclear-electron attractions balanced against letter "delta" as the symbol for "partial," as in the nuclear-nuclear repulsion. A molecule is a neutral species of two or more atoms held together by covalent bonds.

b H-Cl 6

The element carbon (symbol C) is almost always found in nature covalently bonded to other carbon atoms or to a variety of The bond that is formed in hydrogen chloride is termed polar other elements (most commonly H, O , and N). Due to the pres-covalent, and a molecule possessing these partial charges is re-ence of carbon-containing compounds in all living things, the ferred to as "polar." The relative ability of atoms of different chemistry of carbon compounds is known as organic chemistry.

elements to attract electron density is indicated by the property Most high explosives are organic compounds. TNT (trinitrotolu-termed electronegativity. A scale ranking the elements was de-ene), for example, consists of C, H, N, and 0 atoms, with a mo-veloped by Nobel Laureate Linus Pauling. The electronegativity sequence for some of the more common covalent-bond forming ele-lecular formula of C 7H 5N 3O 6. We will encounter other organic compounds in our study of fuels and binders in pyrotechnic mix-ments is given in Table 2.3. Using this sequence, one can assign partial charges to atoms in a variety of molecules; the more tures.

Covalent bonds can form between dissimilar elements, such as electronegative atom in a given bond will bear the partial nega-hydrogen and chlorine.

tive charge, leaving the other atom with a partial positive charge.

1 4

Chemistry of Pyrotechnics

Basic Chemical Principles

TABLE 2.4 Boiling Points of Several Small Molecules rule of solubility is "likes dissolve likes" - a polar solvent such as water is most effective at dissolving polar molecules (such as Boiling point (°C at

sugar) and ionic compounds. A non-polar solvent such as gaso-Compound

Formula

1 atmosphere pressure)

line is most effective at dissolving other non-polar species such as motor oil, but it is a poor solvent for ionic species such as so-Methane

CH,,

-164

dium chloride or potassium nitrate.

Carbon dioxide

78.6

Hydrogen sulfide

H 2S

-60.7

THE MOLE CONCEPT

Water

H ,O

+100

Out of the atomic theory developed by John Dalton and other chemistry pioneers in the 19th century grew a number of important concepts essential to an understanding of all areas of chemistry, including pyrotechnics and explosives. The basic features of the atomic theory are

These partial charges, or dipoles, can lead to intermolecular at-1. The atom is the fundamental building block of matter, and tractions that play an important role in such physical properties consists of a collection of positive, negative, and neutral as melting point and boiling point, and they are quite important subatomic particles.

in determining solubility as well.

The boiling point of water,

Approximately 90 naturally-occurring elements are known 100°C, is quite high when compared to values for other small to exist (additional elements have recently been synthe-molecules (Table 2.4).

sized in the laboratory using nuclear reactions, but these This high boiling point for water can be attributed to strong unstable species are not found in nature).

intermolecular attractions (called "dipole-dipole interactions") of 2. Elements may combine to form more complex species called the type

compounds. The molecule is the fundamental unit of a compound and consists of two or more atoms joined together by chemical bonds.

3. All atoms of the same element are identical in terms of the number of protons and electrons contained in the neutral species. Atoms of the same element may vary in the num-The considerable solubility of polar molecules and many ionic comber of neutrons, and therefore may vary in mass.

pounds in water can be explained by dipole-dipole or ion-dipole 4. The chemical reactivity of an atom depends on the number interactions between the dissolved species and the solvent, water.

of electrons; therefore, the reactivity of all atoms of a given element should be the same, and reproducible, anywhere in the world.

5. Chemical reactions consist of the combination or recombination of atoms, in fixed ratios, to produce new species.

6. A relative scale of atomic weights (as the weighted average The solubility of solid compounds in water, as well as in other of all forms, or isotopes, of a particular element found in solvents, is determined by the competition between attractions in nature) has been developed. The base of this scale is the the solid state between molecules or ions and the solute-solvent assignment of a mass of 12.0000 to the isotope of carbon attractions that occur in solution. A solid that is more attracted containing 6 protons, 6 neutrons, and 6 electrons. An to itself than to solvent molecules will not dissolve. A general atomic weight table can be found in Table 2.2.

Chemistry of Pyrotechnics

Basic Chemical Principles

As electrons are placed into atoms, they successively oc-These concepts permit the chemist to examine chemical reactions cupy higher energy levels, or shells. Electrons in filled and determine the mass relationships that are involved. For ex-levels are unimportant as 'far as chemical reactivity is con-ample, consider the simple pyrotechnic reaction cerned. It is the outer, partially-filled level that determines chemical behavior.

Hence, elements with the same

KC1O,,

4 Mg ; KC1 + 4 MgO

outer-shell configuration display markedly similar chemi-1 mole

4 moles

1 mole

4 moles

cal reactivity.

This phenomenon is called periodicity,

161.2 g

and an arrangement of the elements placing similar ele-138.6 g

97.2 g

74.6 g

ments in a vertical column has been developed - the pe-In a balanced chemical equation, the number of atoms of each riodic table. The alkali metals (lithium, sodium, potas-element on the left-hand, or reactant, side will equal the num-sium, rubidium, and cesium) are one family of the pe-ber of atoms of each element on the right-hand, or product, riodic table - they all have one reactive electron in their side.

The above equation states that one mole of potassium per-outer shell.

The halogens (fluorine, chlorine, bromine,

chlorate (KC10 4 , a reactant) will react with 4 moles of magnesium and iodine) are another common family - all have seven metal to produce one mole of potassium chloride (KCI) and 4 moles electrons in their outer shell and readily accept an eighth of magnesium oxide (MgO).

electron to form a filled level.

In mass terms, 138.6 grams (or pounds, tons, etc.) of potassium perchlorate will react with 97.2 grams (or any other mass The mass of one atom of any element is infinitessimal and is im-unit) of magnesium to produce 74.6 grams of KC1 and 161.2 grams possible to measure on any existing balance. A more convenient of MgO. This mass ratio will always be maintained regardless of mass unit was needed for laboratory work, and the concept of the quantities of starting material involved. If 138.6 grams (1.00

the mole emerged, where one mole of an element is a quantity mole) of KC10 4 and 48.6 grams (2.00 moles) of magnesium are equal to the atomic weight in grams. One mole of carbon, for mixed and ignited, only 69.3 grams (0.50 mole) of the KC1O 4 will example, is 12.01 grams, and one mole of iron is 55.85 grams.

react, completely depleting the magnesium. Remaining as "excess"

The actual number of atoms in one mole of an element has been starting material will be 0.50 mole (69.3 grams) of KC10 4 - there determined by several elegant experimental procedures to be is no magnesium left for it to react with! The products formed 6.02 X 10 23 !

This quantity is known as Avogadro's number, in in this example would be 37.3 grams (0.50 mole) of KC1 and 80.6

honor of one of the pioneers of the atomic theory. One can then grams (2.00 moles) of MgO, plus the 69.3 grams of excess KC10 4 .

see that one mole of carbon atoms (12.01 grams) will contain ex-The preceding example also illustrates the law o f conservation actly the same number of atoms as one mole (55.85 grams) of o f mass. In any normal chemical reaction (excluding nuclear re-iron.

Using the mole concept, the chemist can now go into the actions) the mass of the starting materials will always equal the laboratory and weigh out equal quantities of atoms of the vari-mass of the products (including the mass of any excess reactant).

ous elements.

200 grams of a KC1O 4 /Mg mixture will produce 200 grams of prod-The same concept holds for molecules. One mole of water ucts (which includes any excess starting material).

The "formula" for the preceding illustration involved KC10 4

20) consists of 6.02 X 10 23 molecules and has a mass of 18.0

grams. It contains one mole of oxygen atoms and two moles of and Mg in a 138.6 to 97.2 mass ratio. The balanced mixture -

hydrogen atoms covalently bonded to make water molecules. The with neither material present in excess - should then be 58.8%

molecular weight of a compound is the sum of the respective KC10 4 and 41. 2% Mg by weight. The study of chemical weight atomic weights, taking into account the number of atoms of each relationships of this type is referred to as stoichiometry. A element that comprise the molecule. For ionic compounds, a simi-mixture containing exactly the quantities of each starting ma-lar concept termed formula weight is used.

The formula weight of

terial corresponding to the balanced chemical equation is re-sodium nitrate, NaNO

ferred to as a stoichiometric mixture. Such balanced composi-3 ,

is therefore:

tions are frequently associated with maximum performance in Na + N + 3 O's = 23.0 + 14.0 + 3(16.0) = 85.0 g/mole high-energy chemistry and will be referred to in future chapters.

Chemistry of Pyrotechnics

Basic Chemical Principles

ELECTRON TRANSFER REACTIONS

For the reaction

Oxidation-Reduction Theory

KC1Oy + ? Mg -> KC1 + ? MgO

A major class of chemical reactions involves the transfer of one the oxidation numbers on the various atoms are: or more electrons from one species to another. This process is referred to as an electron-transfer or oxidation-reduction reac-KC10

tion, where the species undergoing electron loss is said to be 4 :

This is an ionic compound, consisting of the potassium ion, K+, and the perchlorate ion, C10,, - . The oxidation num-oxidized while the species acquiring electrons is reduced. Pyro-ber of potassium in K+ will be +1 by rule 2. In technics, propellants, and explosives belong to this chemical re-C104-1 the

4 oxygen atoms are all -2, making the chlorine atom +7, by action category.

rule 4.

The determination of whether or not a species has undergone Mg: Magnesium is present in elemental form as a reactant, a loss or gain of electrons during a chemical reaction can be making its oxidation number 0 by rule 2.

made by assigning "oxidation numbers" to the atoms of the vari-KC1: This is an ionic compound made up of K + and C1- ions, ous reacting species and products, according to the following with respective oxidation numbers of +1 and -1 by rule 2.

simple rules

MgO: This is another ionic compound. Oxygen will be -2 by rule 1, leaving the magnesium ion as +2.

1. Except in a few rare cases, hydrogen is always +1 and oxygen is always -2. Metal hydrides and peroxides are Examining the various changes in oxidation number that occur the most common exceptions. (This rule is applied first -

as the reaction proceeds, one can see that potassium and oxygen it has highest priority, and the rest are applied in de-are unchanged going from reactants to products. Magnesium, creasing priority. )

however, undergoes a change from 0 to +2, corresponding to a 2. Simple ions have their charge as their oxidation number.

loss of two electrons per atom - it has lost electrons, or been For example, Na+ is +1, Cl- is -1, Al +3 is +3, etc. The oxidized. Chlorine undergoes an oxidation number change from oxidation number of an element in its standard state is 0.

+7 to -1, or a gain of 8 electrons per atom - it has been reduced.

3. In a polar covalent molecule, the more electronegative In a balanced oxidation-reduction reaction, the electrons lost atom in a bonded pair is assigned all of the electrons must equal the electrons gained; therefore, four magnesium atoms shared between the two atoms. For example, in H-Cl, (each losing two electrons) are required to reduce one chlorine the chlorine atom is assigned both bonded electrons, atom from the +7 (as C1O,, - ) to -1 (as C1 - ) state. The equation making it identical to C1 - and giving it an oxidation num-is now balanced!

ber of -1. The hydrogen atom therefore has an oxidation number of +1 (in agreement with rule #1 as well).

KC10,, + 4 Mg -> KCI + 4 MgO

4. In a neutral molecule, the sum of the oxidation numbers Similarly, the equation for the reaction between potassium ni-will be 0. For an ion, the sum of the oxidation numbers trate and sulfur can be balanced if one knows that the products on all the atoms will equal the net charge on the ion.

are potassium oxide, sulfur dioxide, and nitrogen gas Examples

?KNO 3 +?S-> ?K 2O+?N 2 +? SO2

Again, analysis of the oxidation numbers reveals that potas-3 (ammonia) :

The 3 hydrogen atoms are all +1 by

rule 1. The nitrogen atom will therefore be -3 by sium and oxygen are unchanged, with values of +1 and -2, re-rule 4.

spectively, on both sides of the equation. Nitrogen changes C0 2

from a value of +5 in the nitrate ion (NO - ) to 0 in elemental 3

(the carbonate ion) : The three oxygen atoms 3

are all -2 by rule 1. Since the ion has a net charge form as N 2 . Sulfur changes from 0 in elemental form to a value of -2, the oxidation number of carbon will be of +4 in SO2 . In this reaction, then, sulfur is oxidized and ni-3(-2) + x = -2, x = +4 by rule 4.

trogen is reduced. To balance the equation, 4 nitrogen atoms,

Chemistry o f Pyrotechnics

Basic Chemical Principles

each gaining 5 electrons, and 5 sulfur atoms, each losing 4 electrons, are required. This results in 20 electrons gained and 20

logically, be the best electron donors, and a combination of a good electrons lost - they're balanced. The balanced equation is electron donor with a good electron acceptor should produce a battery of high voltage. Such a combination will also be a potential therefore:

candidate for a pyrotechnic system. One must bear in mind, however, that most of the values listed in the electrochemistry tables 4KNO 3 +5S- 2K 20+2N 2 +5SO2

are for reactions in solution, rather than for solids, so direct cal-The ratio by weight of potassium nitrate and sulfur correspond-culations can't be made for pyrotechnic systems. Some good ideas ing to a balanced - or stoichiometric - mixture will be 4(101. 1) _

for candidate materials can be obtained, however.

404.4 grams (4 moles) of KNO 3 and 5(32.1) = 160.5 grams (5 moles) A variety of materials of pyrotechnic interest, and their stand-of sulfur. This equals 72% KNO 3 and 28% S by weight. An ability ard reduction potentials at 25°C are listed in Table 2.5. Note the to balance oxidation-reduction equations can be quite useful in large positive values associated with certain oxygen-rich negative working out weight ratios for optimum pyrotechnic performance.

ions, such as the chlorate ion (C10 -3 ), and the large negative values associated with certain active metals such as aluminum (Al).

Electrochemistry

If one takes a spontaneous electron-transfer reaction and sep-THERMODYNAMICS

arates the materials undergoing oxidation and reduction, allow-ing the electron transfer to occur through a good conductor such There are a vast number of possible reactions that the chemist as a copper wire, a battery is created. By proper design, the working in the explosives and pyrotechnics fields can write be-electrical energy associated with reactions of this type can be tween various electron donors (fuels) and electron acceptors (ox-harnessed.

The fields of electrochemistry (e.g. , batteries) idizers). Whether a particular reaction will be of possible use de-and pyrotechnics (e.g., fireworks) are actually very close pends on two major factors:

relatives. The reactions involved in the two areas can look strikingly similar:

1. Whether or not the reaction is spontaneous, or will actually Ag20 + Zn -* 2 Ag + ZnO (a battery reaction) occur if the oxidizer and fuel are mixed together.

2. The rate at which the reaction will proceed, or the time re-Fe20 3 + 2 Al --> 2 Fe + A1 20 3 (a pyrotechnic reaction) quired for complete reaction to occur.

In both fields of research, one is looking for inexpensive, high-energy electron donors and acceptors that will readily yield their energy on demand yet be quite stable in storage.

Spontaneity is determined by a quantity known as the free en-Electrochemists have developed extensive tables listing the ergy change, AG. "A" is the symbol for the upper-case Greek relative tendencies of materials to donate or accept electrons, letter "delta," and stands for "change in."

and these tables can be quite useful to the pyrochemist in his The thermodynamic requirement for a reaction to be sponta-search for new materials. Chemicals are listed in order of de-neous (at constant temperature and pressure) is that the prod-creasing tendency to gain electrons, and are all expressed as ucts are of lower free energy than the reactants, or that AG -

half-reactions in the reduction direction, with the half-reaction the change in free energy associated with the chemical reaction -

be a negative value. Two quantities comprise the free energy of H+ + e } 1/2 H 2

0.000 volts

a system at a given temperature. The first is the enthalpy, or arbitrarily assigned a value of 0.000 volts. All other species are heat content, represented by the symbol H. The second is the measured relative to this reaction, with more readily-reducible entropy, represented by the symbol S, which may be viewed as species having positive voltages (also called standard reduction the randomness or disorder of the system. The free energy of potentials), and less-readily reducible species showing negative a system, G, is equal to H-TS, where T is the temperature of the system on the Kelvin, or absolute, scale. (To convert from values. Species with sizeable negative potentials should then, Celsius to Kelvin temperature, add 273 degrees to the Celsius

2 2

Chemistry of Pyrotechnics

Basic Chemical Principles

TABLE 2.5

Standard Reduction Potentials

value.)

The free energy change accompanying a chemical reaction at constant temperature is therefore given by Standard potential

Half-reaction

@25 0 C, in voltsa

AG = G(products) - G(reactants) = AH - TAS

(2.1)

For a chemical reaction to be spontaneous, or energetically fa-3 N

-3.1

2 + 2H+ + 2 e -> 2 HN 3

vorable, it is desirable that 6H, or the enthalpy change, be a Li+ + e - Li

-3.045

negative value, corresponding to the liberation of heat by the reaction.

Any chemical process that liberates heat is termed exo-H

0+3e- B +4OH -

-2.5

2B0 3

+ H 2

thermic, while a process that absorbs heat is called endothermic.

Mg+ 2

AH values for many high-energy reactions have been experimen-

+ 2 e -• Mg

-2.375

tally determined as well as theoretically calculated.

The typical

HPO =

-1.71

units for AH, or heat of reaction, are calories/mole or calories/

+ 2 H 2O + 3e + P + 5 OH -

gram.

The new International System of units calls for energy Al

+ 3 e + Al (in dil. NaOH soln. )

-1.706

values to be given in joules, where one calorie = 4.184 joules.

TiO

Most thermochemical data are found with the calorie as the unit, 2 +4H++4e+Ti+2H 2 0

-0.86

and it will be used in this book in most instances. Some typical Si0

-0.84

2 +4H++4e+ Si +2H 0

AH values for pyrotechnics are given in Table 2.6.

Note:

kcal = 1 kilocalorie = 1,000 calories.

S+2e+ S =

-0.508

It is also favorable to have the entropy change, AS, be a posi-Bi

-0.46

tive value, making the -TAS term in equation 2.1 a negative value.

2 0 3 +3H 20+6e-> 2Bi+6OH

A positive value for AS corresponds to an increase in the random-WO 3 + 6 H + + 6 e - W + 3 H 2O

-0.09

ness or disorder of the system when the reaction occurs.

As a

general rule, entropy follows the sequence:

Fe' 3 + 3e- Fe

-0.036

S(solid) < S(liquid) << S(gas)

2H + +2e + H2

0.000

Therefore, a process of the type solids -- gas (common to many N0 - +

+0.01

H 20+2e+N0 2 + 2 OH

high-energy systems) is particularly favored by the change in entropy occurring upon reaction. Reactions that evolve heat and H

+0.45

2 SO 3 +4H + +4e-> S+3H 2 0

form gases from solid starting materials should be favored ther-N0 -

+ 4 H + + 3 e + NO + 2 H 2 O

+0.96

modynamically and fall in the "spontaneous" category. Chemical processes of this type will be discussed in subsequent chapters.

10 -

+1.195

+ 6 H + + 6 e - I - + 3 H 2O

HCr0

+1.195

+ 7 H + + 3 e - Cr

4 H 2O

Heat of Reaction

C1O,,

+8H++8e+Cl + 4 H 2 O

+1. 37

It is possible to calculate a heat of reaction for a high-energy system by assuming what the reaction products will be and then using Br0

+1.44

+ 6 H + + 6 e + Br + 3 H 2O

available thermodynamic tables of heats of formation.

"Heat of

C10

+1.45

formation" is the heat associated with the formation of a chemi-3

+6H + +6e- C1 +3H 20

cal compound from its constituent elements. For example, for Pb0

+1.46

2 +4H + +2e+Pb +2 +2H 20

the reaction

Mn0 4 + 8H++ 5e- Mn +2 + 4 H 2 O

+1.49

2 Al + 3/2 0 2 + A1 20 3

AH is -400.5 kcal/mole of

A120 3, and this value is therefore the

Reference 1.

heat of formation (AHf) of aluminum oxide (A1 20 3). The reaction

Chemistry of Pyrotechnics

Basic Chemical Principles

TABLE 2.6 Typical AH Values for "High-Energy" Reactions The net heat change associated with the overall reaction can then be calculated from

Composition

A H

6H(reaction) = EAH

(2.2)

f (products) - l lH f (reactants)

(% by weight)

(kcal/gram)a

Application

(where E = "the sum of")

KC1O,,

2.24

Photoflash

This equation sums up the heats of formation of all of the products from a reaction, and then subtracts from that value the heat NaNO 3

2.00

White light

required to dissociate all of the starting materials into their ele-Al

ments.

The difference between these two values is the net heat Fe203

0.96

Thermite (heat)

change, or heat of reaction. The heats of formation of a number Al

of materials of interest to the high-energy chemist may be found in Table 2.7.

All values given are for a reaction occurring at KNO 3

0.66

Black powder

25°C (298 K).

Example 1

KC1O 3

0.61

Red light

Consider the following reaction, balanced using the "oxidation SrCO 3

numbers" method

Shellac

Reaction

KCIO,, + 4 Mg

- KC1

+ 4 MgO

KC1O 3

0.38

Red smoke

Grams

138.6

97.2

74.6

161.2

Lactose

Heat of formation

-103.4

4(0)

-104.4

4(-143.8)

Red dye

(kcal/mole x # of moles)

AH(reaction) = EAHf(products) - EAHf(reactants) Reference 2. All values represent heat released by the reaction.

_ [-104.4 + 4(-143.8)] - [-103.4 + 4(0)]

_ -576.2 kcal/mole KC10,,

_ -2.44 kcal/gram of stoichiometric mixture (obtained by dividing -576.2 kcal by 138.6 + 97.2 = 235.8

grams of starting material).

of 2.0 moles (54.0 grams) of aluminum with oxygen gas (48.0

grams) to form A1 20 3 (1.0 mole, 102.0 grams) will liberate 400.5

xampe :

kcal of heat - a sizeable amount! Also, to decompose 102.0 grams Reaction

4 KNO

of A1

+ 5 C - 2 K 20

+ 2 N 2 +5CO 2

20 3 into 54.0 grams of aluminum metal and 48.0 grams of oxy-Grams

404.4

188.4

220

gen gas, one must put 400.5 kcal of heat into the system - an Heat of formation

4(-118.2)

5(0)

2(-86.4)

2(0)

5(-94.1)

amount equal in magnitude but opposite in sign from the heat of (kcal/mole x # of moles)

formation.

The heat of formation of any element in its standard state at 25°C will therefore be 0 using this system.

AH(reaction) = EAHf(products) - EAHf(reactants) A chemical reaction can be considered to occur in two steps:

= [ 2(-86.4) + 0 + 5(-94.1)] - [4(-118.2) + 5(0)]

= -643.3 - (-472.8)

Decomposition of the starting materials into their constitu-

= -170.5 kcal/equation as written (4 moles KNO 3) ent elements, followed by

= -42.6 kcal/mole KNO 3

Subsequent reaction of these elements to form the desired _ -0.37 kcal/gram of stoichiometric mixture (-170.5

products.

kcal per 464.4 grams)

Basic Chemical Principles 27

Chemistry of Pyrotechnics

TABLE 2. 7 Standard Heats of Formation at 25°C

TABLE 2.7 (continued)

L Hformation

o H form ation

Compound

Formula

(kcal /mole )a

Compound

Formula

(kcal /mole) a

REACTION PRODUCTS

OXIDIZERS

Aluminum oxide

A1 2 0 3

-400.5

Ammonium nitrate

NH,,NO 3

-87.4

Barium oxide

BaO

-133.4

Ammonium perchlorate

NH 4ClO,,

-70.58

Boron oxide

B 20 3

-304.2

Barium chlorate (hydrate)

Ba(C1O 3 ) 2 H 20

-184.4

Carbon dioxide

CO 2

-94.1

Barium chromate

BaCr0 4

-345.6

Carbon monoxide

-26.4

Barium nitrate

Ba(NO 3 ) 2

-237.1

Chromium oxide

Cr 2O 3

-272.4

Barium peroxide

Ba0 2

-151.6

Lead oxide (Litharge)

PbO

-51.5

Iron oxide

Fe 2O 3

-197.0

Magnesium oxide

MgO

-143.8

Iron oxide

Fe 3 O 4

-267.3

Nitrogen

N 2

Lead chromate

PbCr0 4

- 217. 7b

Phosphoric acid

H 3PO4

-305.7

Lead oxide (red lead)

Pb 30 4

-171.7

Potassium carbonate

K 2 CO 3

-275.1

Lead peroxide

PbO 2

-66.3

Potassium chloride

KC1

-104.4

Potassium chlorate

KC10 3

-95.1

Potassium oxide

K ,O

-86.4

Potassium nitrate

KNO 3

-118.2

Potassium sulfide

K ,S

-91.0

Potassium perchlorate

KC1O 4

-103.4

Silicon dioxide

Si02

-215.9

Sodium nitrate

NaNO 3

-111.8

Sodium chloride

NaCl

-98.3

Strontium nitrate

Sr(NO 3 ) 2

-233.8

Sodium oxide

N a.0

-99.0

Strontium oxide

SrO

-141.5

FUELS

Titanium dioxide

TiO 2

-225

Elements

Water

H ,O

-68.3

Zinc chloride

ZnC1 2

-99.2

Aluminum

Boron

Iron

Reference 1.

Magnesium

bReference 4.

Phosphorus (red)

-4.2

cReference 2.

Silicon

Titanium

Organic Compoundsc

RATES OF CHEMICAL REACTIONS

Lactose (hydrate)

C12H22 0 11'H2O

-651

Shellac

C16H24 0 5

-227

The preceding section discussed how the chemist can make a ther-Hexachloroethane

C ' C1'

- 54

modynamic determination of the spontaneity of a chemical reaction.

Starch (polymer)

(C6H1005)n

-227 (per unit)

However, even if these calculations indicate that a reaction should Anthracene

C14H10

+32

be quite spontaneous (the value for oG is a large, negative num-Polyvinyl chloride (PVC)

(-CH 2CHC1-) n

-23 (per unit)b

ber), there is no guarantee that the reaction will proceed rapidly

2 8

Chemistry o f Pyrotechnics Basic Chemical Principles

when the reactants are mixed together at 25°C (298 K). For ex-A+ B -- C+D

ample, the reaction

Wood + 0 2 } CO 2 + H O

has a large, negative value for AG at 25 0 C. However (fortunately!) wood and oxygen are reasonably stable when mixed together at 25°C (a typical room temperature). The explanation of this thermodynamic mystery lies in another energy concept known as the energy of activation.

This term represents that amount of en-

ergy needed to take the starting materials from their reasonably FREE

stable form at 25°C and convert them to a reactive, higher-energy ENERGY,

excited state. In this excited state, a reaction will occur to form G

the anticipated products, with the liberation of considerable energy - all that was required to reach the excited state, plus more.

Figure 2.1 illustrates this process.

The rate of a chemical reaction is determined by the magnitude C+ D

of this required activation energy, and rate is a temperature-de-

( PRODUCTS)

pendent phenomenon. As the temperature of a system is raised, an exponentially-greater number of molecules will possess the necessary energy of activation. The reaction rate will therefore increase accordingly in an exponential fashion as the temperature rises.

This is illustrated in Figure 2.2.

Much of the pioneering

work in the area of reaction rates was done by the Swedish chem-REACTION PROGRESS

ist Svante Arrhenius, and the equation describing this rate-temperature relationship is known as the Arrhenius Equation FIG. 2.1 The free energy, G, of a chemical system as reactants Ea/RT

A and B convert to products C and D. A and B must first acquire k = Ae

(2.3)

sufficient energy ("activation energy") to be in a reactive state.

As products C and D are formed, energy is released and the where

final energy level is reached.

The net energy change, AG,

the rate constant for a particular reaction at temperature corresponds to the difference between the energies of the prod-T. (This is a constant representing the speed of the re-ucts and reactants. The rate at which a reaction proceeds is de-action, and is determined experimentally.)

termined by the energy barrier that must be crossed - the acti-A = a temperature-independent constant for the particular revation energy.

action, termed the "pre-exponential factor."

E a = the activation energy for the reaction.

R = a universal constant known as the "ideal gas constant."

T = temperature, in degrees Kelvin.

If the natural logarithm On) of both sides of equation (2.3) be obtained, with slope of -Ea /R .

Activation energies can be

is taken, one obtains

obtained for chemical reactions through such experiments. The Arrhenius Equation, describing the rate-temperature relation-In k = In A - Ea/RT

(2.4)

ship, is of considerable significance in the ignition of pyro-Therefore, if the rate constant, k, is measured at several tem-technics and explosives, and it will be referred to in subse-peratures and in k versus l /T is plotted, a straight line should quent chapters.

3 0

Chemistry of Pyrotechnics

Basic Chemical Principles

RATE,

(MOLES/SEC)

Picric acid

FIG. 2. 3 Many "unstable" organic compounds are used as explosives. These molecules contain internal oxygen, usually bonded TEMPERATURE, K

to nitrogen, and undergo intramolecular oxidation-reduction to form stable products - carbon dioxide, nitrogen, and water.

FIG. 2.2 The effect of temperature on reaction rate. As the tem-The "mixing" of oxidizer and fuel is achieved at the molecular perature of a chemical system is increased, the rate at which that level, and fast rates of decomposition can be obtained.

system reacts to form products increases exponentially.

large positive numbers indicate electron deficiency. It is there-ENERGY-RICH BONDS

fore not surprising that structures with such.bonding arrange-ments are particularly reactive as electron acceptors (oxidizers).

Certain covalent chemical bonds (such as N-O and Cl-O) are par-It is for similar reasons that many of the nitrated carbon-contain-ticularly common in the high-energy field. Bonds between two ing ("organic") compounds, such as nitroglycerine and TNT, are highly electronegative atoms tend to be less stable than ones be-so unstable (Figure 2.3). The nitrogen atoms in these molecules tween atoms of differing electronegativity. The intense competi-want to accept electrons to relieve bonding stress, and the car-tion for the electron density in a bond such as Cl-O is believed bon atoms found in the same molecules are excellent electron do-to be responsible for at least some of this instability. A modern nors. Two very stable gaseous (high entropy) chemical species, chemical bonding theory known as the "molecular orbital theory"

N2 and C02 , are produced upon decomposition of most nitrated predicts inherent instability for some common high-energy spe-carbon-containing compounds, helping to insure a large, nega-cies. The azide ion,

and the fulminate ion, CNO - , are ex-

N3-,

tive value for AG for the decomposition (therefore making it a amples of species whose unstable behavior is explainable using spontaneous process).

this approach [ 3] .

These considerations make it mandatory that anyone working In structures such as the nitrate ion, N0 3 , and the perchlor-with nitrogen-rich carbon-containing compounds or with nitrate, ate ion, C10 - , a highly electronegative atom has a large, positive 4

perchlorate, and similar oxygen-rich negative ions must use oxidation number (+5 for N in

+7 for Cl in C1O,,) . Such

N03-1

extreme caution in the handling of these materials until their

3 2

Chemistry of Pyrotechnics

Basic Chemical Principles

properties have been fully examined in the laboratory. Elevated TABLE 2.8 Melting Points of Some Common Oxidizers temperatures should also be avoided when working with potentially-unstable materials, because of the rate-temperature rela-Melting point,

tionship that is exponential in nature. A non-existent or sluggish process can become an explosion when the temperature of Oxidizer

Formula

°C a

the system is sharply increased.

Potassium nitrate

KNO 3

334

Potassium chlorate

KC10 3

356

STATES OF MATTER

Barium nitrate

Ba(N03)2

592

With few exceptions the high-energy chemist deals with materials Potassium perchlorate

KC1O,,

610

that are in the solid state at normal room temperature. Solids mix very slowly with one another, and hence they tend to be Strontium nitrate

Sr(N0 3 ) 2

570

quite sluggish in their reactivity.

Rapid reactivity is usually

Lead chromate

PbCr0

844

associated with the formation, at higher temperatures, of liquids or gases. Species in these states can diffuse into one another Iron oxide

Fe 20 3

1565

more rapidly, leading to accelerated reactivity.

In pyrotechnics, the solid-to-liquid transition appears to be a Reference 1.

of considerable importance in initiating a self-propagating reaction.

The oxidizing agent is frequently the key component in such mixtures, and a ranking of common oxidizers by increasing melting point bears a striking resemblance to the reactivity se-This equation is obeyed quite well by the inert gases (helium, quence for these materials (Table 2.8).

neon, etc.) and by small diatomic molecules such as H 2 and N 2 .

Molecules possessing polar covalent bonds tend to have strong Gases

intermolecular attractions and usually deviate from "ideal" beha-On continued heating, a pure material passes from the solid to vior.

Equation 2.5 remains a fairly good estimate of volume and liquid to vapor state, with continued absorption of heat. The pressure even for these polar molecules, however. Using the ideal gas equation, one can readily estimate the pressure pro-volume occupied by the vapor state is much greater than that duced during ignition of a confined high-energy composition.

of the solid and liquid phases. One mole (18 grams) of water For example, assume that 200 milligrams (0.200 grams) of occupies approximately 18 milliliters (0.018 liters) as a solid or liquid.

One mole of water vapor, however, at 100°C (373 K) black powder is confined in a volume of 0. 1 milliliter. Black occupies approximately 30.6 liters at normal atmospheric pres-powder burns to produce approximately 50% gaseous products sure.

The volume occupied by a gas can be estimated using the and 50% solids.

Approximately 1. 2 moles of permanent gas are i deal gas equation

produced per 100 grams of powder burned (the gases are mainly (equation 2.5).

N 2 , CO 2 , and CO) [5]. Therefore, 0.200 grams should produce V = nRT /P

(2.5)

0.0024 moles of gas, at a temperature near 2000 K. The expected pressure is:

where

P _ (0.0024 mole) (0.0821 liter-atm /deg-mole) (2000deg) V = volume occupied by the gas, in liters

(0.0001 liter)

n = # moles of gas

R = a constant, 0.0821 liter-atm /deg-mole

= 3941 atm!

T = temperature, in K

Needless to say, the casing will rupture and an explosion will P = pressure, in atmospheres

be observed. Burning a similar quantity of black powder in the

Chemistry of Pyrotechnics

Basic Chemical Principles

open, where little pressure accumulation occurs, will produce a external pressure acting on the liquid surface, boiling occurs.

slower, less violent (but still quite vigorous!) reaction and no For solids and liquids to undergo sustained burning, the pres-explosive effect. This dependence of burning behavior on de-ence of a portion of the fuel in the vapor state is required.

gree of confinement is an important characteristic of pyrotechnic mixtures, and distinguishes them from true high explosives.

The Solid State

Liquids

The solid state is characterized by definite shape and volume.

The observed shape will be the one that maximizes favorable Gas molecules are widely separated, travelling at high speeds interactions between the atoms, ions, or molecules making up while colliding with other gas molecules and with the walls of the structure. The preferred shape begins at the atomic or their container. Pressure is produced by these collisions with molecular level and is regularly repeated throughout the solid, the walls and depends upon the number of gas molecules present producing a highly-symmetrical, three-dimensional form called as well as their kinetic energy. Their speed, and therefore their a crystal. The network produced is termed the crystalline lot -

kinetic energy, increases with increasing temperature.

t ice .

As the temperature of a gas system is lowered, the speed of Solids lacking an ordered, crystalline arrangement are termed the molecules decreases. When these lower-speed molecules col-amorphous materials, and resemble rigid liquids in structure and lide with one another, attractive forces between the molecules be-properties. Glass (Si0 2) is the classic example of an amorphous come more significant, and a temperature will be reached where solid. Such materials typically soften on heating, rather than condensation occurs - the vapor state converts to liquid. Di-showing a sharp melting point.

pole-dipole attractive forces are most important in causing con-In the crystalline solid state, there is little vibrational or densation, and molecules with substantial partial charges, re-translational freedom, and hence diffusion into a crystalline sulting from polar covalent bonds, typically have high condensa-lattice is slow and difficult. As the temperature of a solid is tion temperatures. (Condensation temperature will be the same raised by the input of heat, vibrational and translational motion as the boiling point of a liquid, approached from the opposite di-increases. At a particular temperature - termed the melting rection. )

point - this motion overcomes the attractive forces holding the The liquid state has a minimum of order, and the molecules lattice together and the liquid state is produced. The liquid have considerable freedom of motion. A drop of food coloring state, on cooling, returns to the solid state as crystallization placed in water demonstrates the rapid diffusion that can occur occurs and heat is released by the formation of strong attrac-in the liquid state. The solid state will exhibit no detectable tive forces.

diffusion. If this experiment is tried with a material such as The types of solids, categorized according to the particles iron, the liquid food coloring will merely form a drop on the sur-that make up the crystalline lattice, are listed in Table 2.9.

face of the metal.

The type of crystalline lattice formed by a solid material de-At the liquid surface, molecules can acquire high vibrational pends on the size and shape of the lattice units, as well as on and translational energy from their neighbors, and one will oc-the nature of the attractive forces. Six basic crystalline sys-casionally break loose to enter the vapor state. This phenomenon tems are possible [6]

of vapor above a liquid surface is termed vapor pressure, and will lead to gradual evaporation of a liquid unless the container is covered. In this case, an equilibrium is established between 1. Cubic: three axes of equal length, intersecting at all the molecules entering the vapor state per minute and the mole-right angles

cules recondensing on the liquid surface. The pressure of gas 2. Tetragonal: three axes intersecting at right angles; only molecules above a confined liquid is a constant for a given ma-two axes are equal in length

terial at a given temperature, and is known as the equilibrium 3. Hexagonal: three axes of equal length in a single plane vapor pressure. It increases exponentially with increasing tem-intersecting at 60 0 angles; a fourth axis of different length perature. When the vapor pressure of a liquid is equal to the is perpendicular to the plane of the other three

Chemistry of Pyrotechnics

Basic Chemical Principles

TABLE 2.9 Types of Crystalline Solids

TABLE 2.10 Thermal Conductivity Values for Solidsa Units

Thermal conductivity (X 10),

Type of

comprising

Material

cal/see-cm-IC

solid

crystal lattice

Attractive force

Examples

Copper

910

Ionic

Positive and

Electrostatic attrac- KNO 3 , NaCl

Aluminum

500

negative ions

tion

Iron

150

Molecular Neutral mole-

Dipole-dipole attrac- CO 2 ("dry ice"), cules

tions, plus weaker, sugar

Glass

2.3

non-polar forces

Oak wood

0.4

Covalent

Atoms

Covalent bonds

Diamond (carbon)

Paper

0.3

Metallic

Metal atoms

Dispersed electrons Fe, Al, Mg

Charcoal

0.2

attracted to nu-

merous metal atom

nuclei

a Reference 8.

4. Rhombic: three axes of unequal length, intersecting at melting point of the solid, with the solid } liquid transition occur-right angles

ring over a broad range rather than displaying the sharp melting 5. Monoclinic: three axes of unequal length, two of which observed with a purer material.

Melting behavior thereby pro-

intersect at right angles

vides a convenient means of checking the purity of solids.

6. Triclinic : three axes of unequal length, none of which An important factor in the ignition and propagation of burning intersect at right angles

of pyrotechnic compositions is the conduction of heat along a column of the mixture. Hot gases serve as excellent heat carriers, To this point, our model of the solid state has suggested a but frequently the heat must be conducted by the solid state, placement of every lattice object at the proper site to create a ahead of the reaction zone. Heat can be transferred by molecu-

"perfect" three-dimensional crystal. Research into the actual lar motion as well as by free, mobile electrons [6]. The thermal structure of solids has shown that crystals are far from per-conductivity values of some common materials are given in Table 2.10.

fect, containing a variety of types of defects. Even the purest Examining this table, one can readily see how the pres-crystals modern chemistry can create contain large numbers of ence of a small quantity of metal powder in a pyrotechnic compo-impurities and "misplaced" ions, molecules, or atoms in the lat-sition can greatly increase the thermal conductivity of the mixture, and thereby increase the burning rate.

tice. These inherent defects can play an important role in the reactivity of solids by providing a mechanism for the transport Electrical conductivity can also be an important consideration in pyrotechnic theory [7].

of electrons and heat through the lattice. They also can greatly This phenomenon results from the

enhance the ability of another substance to diffuse into the lat-presence of mobile electrons in the solid that migrate when an electrical potential is applied across the material.

tice, thereby again affecting reactivity [7).

Metals are

A commonly-observed phenomenon associated with the pres-the best electrical conductors, while ionic and molecular solids ence of impurities in a crystalline lattice is a depression in the are generally much poorer, serving well as insulators.

Chemistry of Pyrotechnics

Basic Chemical Principles

(KOH), and calcium hydroxide, Ca(OH)

ACIDS AND BASES

2 .

Ammonia (NH 3 ) is a

weak base, capable of reacting with H+ to form the ammonium ion,

An acid is commonly defined as a molecule or ion that can serve as N H,

Acids catalyze a variety of chemical reactions, even when pres-a hydrogen ion (H + ) donor. The hydrogen ion is identical to the ent in small quantity. The presence of trace amounts of acidic ma-proton - it contains one proton in the nucleus, and has no elec-terials in many high-energy compounds and mixtures can lead to trons surrounding the nucleus. H + is a light, mobile, reactive instability. The chlorate ion, C10 - , is notoriously unstable in species. A base is a species that functions as a hydrogen ion 3

the presence of strong acids. Chlorate-containing mixtures will acceptor. The transfer of a hydrogen ion (proton) from a good usually ignite if a drop of concentrated sulfuric acid is added.

donor to a good acceptor is called an acid/base reaction. Materi-Many metals are also vulnerable to acids, undergoing an oxi-als that are neither acidic nor basic in nature are said to be neu-dation /reduction reaction that produces the metal ion and hydro-tral

gen gas. The balanced equation for the reaction between HCl Hydrogen chloride (HC1) is a gas that readily dissolves in wa-and magnesium is

ter. In water, HCl is called hydrochloric acid and the HC1 molecule serves as a good proton donor, readily undergoing the re-Mg + 2 HC1 } Mg +2 + H 2 + 2 CI- +heat

action

Consequently, most metal-containing compositions must be free HC1 , H+ + Cl -

of acidic impurities or extensive decomposition (and possibly ignition) may occur.

to produce a hydrogen ion and a chloride ion in solution. The As protection against acidic impurities, high-energy mixtures concentration of hydrogen ions in water can be measured by a will frequently contain a small percentage of a neutralizer. So-variety of methods and provides a measure of the acidity of an dium bicarbonate (NaHCO

aqueous system. The most common measure of acidity is pH, a 3 ) and magnesium carbonate (MgCO

-23 )

are two frequently-used materials. The carbonate ion, C0

number representing the negative common logarithm of the hy-3

re-

acts with H +

drogen ion concentration

-2

2H+ +CO

i H

pH = -log [H+]

2O+CO 2

to form two neutral species - water and carbon dioxide.

If a solution also contains hydroxide ion (OH - ), a good proton ac-Boric acid (H

ceptor, the reaction

3 BO 3 ) - a solid material that is a weak H + donor -

is sometimes used as a neutralizer for base-sensitive compositions.

H+ + OH + H

Mixtures containing aluminum metal and a nitrate salt are notably 2 O

sensitive to excess hydroxide ion, and a small percentage of boric occurs, forming water - a neutral species. The overall reaction acid can be quite effective in stabilizing such compositions.

is represented by an equation such as

HCl + NaOH -> H 2O + NaCl

I NSTRUMENTAL ANALYSIS

Acids usually contain a bond between hydrogen and an electronegative element such as F, 0, or Cl. The electronegative ele-Modern instrumental methods of analysis have provided scientists ment pulls electron density away from the hydrogen atom, giving with a wealth of information regarding the nature of the solid state it partial positive character and making it willing to leave as H + .

and the reactivity of solids. Knowledge of the structure of solids The presence of additional F, 0, and Cl atoms in the molecule and an ability to study thermal behavior are essential to an under-further enhances the acidity of the species. Examples of strong standing of the behavior of high-energy materials.

acids include sulfuric acid

hydrochloric acid (HC1),

(H2SO4),

X-ray crystallography has provided the crystal type and lat-perchloric acid (HC10,,), and nitric acid (HNO 3).

Most of the common bases are ionic compounds consisting of a tice dimensions for numerous solids. In this technique, high-energy x-rays strike the crystal and are diffracted in a pattern positive metal ion and the negatively-charged hydroxide ion, OH - .

characteristic of the particular lattice type.

Examples include sodium hydroxide (NaOH), potassium hydroxide Complex mathematical

Chemistry of Pyrotechnics

analysis can convert the diffraction pattern into the actual crystal structure. Advances in computer technology have revolutionized this field in the past few years. Complex structures, formerly requiring months or years to determine, can now be analyzed in short order. Even huge protein and nucleic acid chains can be worked out by the crystallographer [9].

Differential thermal analysis (DTA) has provided a wealth of information regarding the thermal behavior of pure solids as well as solid mixtures [10] . Melting points, boiling points, transitions from one crystalline form to another, and decomposition temperatures can be obtained for pure materials. Reaction temperatures can be determined for mixtures, such as ignition temperatures for pyrotechnic and explosive compositions.

Differential thermal analysis detects the absorption or release of heat by a sample as it is heated at a constant rate from room temperature to an upper limit, commonly 500°C. Any heat-absorbing changes occurring in the sample (e.g. , melting or boiling) will be detected, as will processes that evolve heat (e.g. , exothermic reactions). These changes are detected by continually comparing the temperature of the sample with that of a thermally-inert reference material (frequently aluminum oxide) FIG. 2.4

The thermogram for pure 2,4,6-trinitrotoluene (TNT).

that undergoes no phase changes or reactions over the tempera-The major features are an endotherm corresponding to melting at ture range being studied. Both sample and reference are placed 81°C and an exothermic decomposition peak beginning near 280°.

in glass capillary tubes, a thermocouple is inserted in each, and The x axis represents the temperature of the heating block in de-the tubes are placed in a metal heating block. Current is applied grees centigrade. The y axis indicates the difference in tempera-to the electric heater to produce a linear temperature increase ture, AT, between the sample and an identically-heated reference (typically 20-50 degrees/minute) [7].

solid, typically glass beads or aluminum oxide.

If an endothermic (heat-absorbing) process occurs, the sample will momentarily become cooler than the reference material; the small temperature difference is detected by the pair of thermocouples and a downward deflection, termed an endotherm, is produced in the plot of AT (temperature difference between sample of rapid heating of a confined sample, and must be recognized as and reference) versus T (temperature of the heating block).

such.

Evolution of heat by the sample will similarly produce an upward Some representative thermograms of high-energy materials are deflection, termed an exotherm. The printed output produced by shown in Figures 2.4-2.6.

the instrument, a thermogram, is a thermal "fingerprint" of the material being analyzed. Thermal analysis is quite useful for determining the purity of materials; this is accomplished by exam-LIGHT EMISSION

ining the location and "sharpness" of the melting point. DTA is also useful for qualitative identification of solid materials, by com-The pyrotechnic phenomena of heat, smoke, noise, and motion are paring the thermal pattern with those of known materials. Reac-reasonably easy to comprehend. Heat results from the rapid re-tion temperatures, including the ignition temperatures of high-lease of energy associated with the formation of stable chemical energy materials, can be quickly (and safely) measured by ther-bonds during a chemical reaction. Smoke is produced by the dis-mal analysis. These temperatures will correspond to conditions persion in air of many small particles during a chemical reaction.

Chemistry of Pyrotechnics

Basic Chemical Principles

FIG. 2.5 Ballistite, a "smokeless powder" consisting of 60% nitrocellulose and 40% nitroglycerine, produces a thermogram with no FIG. 2.6 Black powder was the first "modern" high-energy mix-transitions detectable prior to exothermic decomposition above ture, and it is still used in a variety of pyrotechnic applications.

150 0C.

It is an intimate blend of potassium nitrate (75%), charcoal (15%), I

and sulfur (10%). The thermogram for the mixture shows endotherms near 105° and 119°C corresponding to a solid-solid phase transition and melting for sulfur, a strong endotherm near 130°

representing a solid-solid transition in potassium nitrate, and a Noise is produced by the rapid generation of gas at high tempera-violent exotherm near 330°C where ignition of the mixture occurs.

ture, creating waves that travel through air at the "speed of sound," 340 meters/second. Motion can be produced if you direct the hot gaseous products of a pyrotechnic reaction out through an We can represent these allowed electronic energies by a diagram exit, or nozzle. The thrust that is produced can move an object of considerable mass, if sufficient propellant is used.

such as Figure 2.7.

The theory of color and light production, however, involves Logic suggests that an electron will occupy the lowest energy the energy levels available for electrons in atoms and molecules, level available, and electrons will successively fill these levels as according to the beliefs of modern chemical theory. In an atom they are added to an atom or molecule. "Quantum mechanics"

or molecule, there are a number of "orbitals" or energy levels restricts all orbitals to a maximum of two electrons (these two have opposite "spins" and do not strongly repel one another), that an electron may occupy. Each of these levels corresponds to a discrete energy value, and only these energies are possible.

and hence a filling process occurs. The filling pattern for the The energy is said to be quantized, or restricted to certain val-sodium atom (sodium is atomic number 11 - therefore there will ues that depend on the nature of the particular atom or molecule.

be 11 electrons in the neutral atom) is shown in Figure 2.7).

Basic Chemical Principles

This energy can be lost as heat upon return to the ground state, or it can be released as a unit, or "photon," of light.

Light, or electromagnetic radiation, has both wave and particle or unit character associated with its behavior. Wavelengths range from very short (10 -12 meters) for the "gamma rays" that accompany nuclear decay to quite long (10 meters) for radio waves.

All light travels at the same speed in a vacuum, with a value of 3 X 108 meters/second - the "speed of light." This value can be used for the speed of light in air as well.

The wavelength of light can now be related to the frequency, or number of waves passing a given point per second, using the speed of light value:

frequency (v) = speed (c)/wavelength (A)

(2.6)

(waves/second) = (meters/second) /(meters /wave) The entire range of wavelengths comprising "light" is known as the electromagnetic spectrum (Figure 2.8).

FIG. 2.7 The energy levels of the sodium atom. The sodium atom contains 11 electrons. These electrons will successively fill the lowest available energy levels in the atom, with a maximum popu-ULTRAVIOLET

lation of two electrons in any given "orbital." The experimentally-and VISIBLE

determined energy level sequence is shown in this figure, with the 11th (and highest-energy) electron placed in the 3s level. The lowest vacant level is a 3p orbital. To raise an electron from the 3s to the 3p level requires 3.38 X 10 -19 joules of energy. This energy corresponds to light of 589 nanometer wavelength - the yellow portion of the visible spectrum. Sodium atoms heated to high temperature will emit this yellow light as electrons are thermally excited to the 3p level, and then return to the 3s level and give off the excess energy as yellow light.

ULTRAVIOLET

200-380 nm (1nm = 10-9m)

VISIBLE

380.780nm

When energy is put into a sodium atom, in the form of heat or FIG. 2.8 The electromagnetic spectrum. The various regions of light, one means of accepting this energy is for an electron to be the electromagnetic spectrum correspond to a wide range of wave-

"promoted" to a higher energy level. The electron in this "ex-lengths, frequencies, and energies. The radiofrequency range is cited state" is unstable and will quickly return to the ground at the long-wavelength , low energy end, with gamma rays at the state with the release of an amount of energy exactly equal to short-wavelength, high-frequency, high-energy end. The "vis-the energy difference between the ground and excited states.

ible" region - that portion of the spectrum perceived as color by For the sodium atom, the difference between the highest occu-the human visual system -- falls in the narrow region from 380-pied and lowest unoccupied levels is 3.38 X 10 -19 joules/atom.

780 manometers (1 nm = 10 -9 m).

Chemistry of Pyrotechnics

Basic Chemical Principles

transitions possible for the particular atom. The pattern is char-We can readily tell that light is a form of energy by staying acteristic for each element and can be used for qualitative iden-out in the sun for too long a time. Elegant experiments by Einstein and others clearly showed that the energy associated with tification purposes.

light was directly proportional to the frequency of the radiation:

• = by = h c/A

(2.7)

Molecular Emission

A similar phenomenon is observed when molecules are vaporized where

and thermally excited. Electrons can be promoted from an oc-

• = the energy per light particle ("photon") cupied ground electronic state to a vacant excited state; when

• = a constant, Planck's Constant, 6.63 X 10 -34 joule-seconds an electron returns to the ground state, a photon of light may v = frequency of light (in waves - "cycles" - per second) be emitted.

• = speed of light (3 X 10 8 meters /second) Molecular spectra are usually more complex than atomic spec-A = wavelength of light (in meters)

tra. The energy levels are more complex, and vibrational and rotational sublevels superimpose their patterns on the electronic spectrum. Bands are generally observed rather than the sharp This equation permits one to equate a wavelength of light with the lines seen in atomic spectra. Emission intensity again increases energy associated with that particular radiation. For the sodium as the flame temperature is raised. However, one must be con-atom, the wavelength of light corresponding to the energy differ-cerned about reaching too high a temperature and decomposing ence of 3.38 X 10 -19 joules between the highest occupied and low-the molecular emitter; the light emission pattern will change if est unoccupied electronic energy levels should be: this occurs. This is a particular problem in achieving an in-

• =hd=hc/A

tense blue flame. The best blue light emitter - CuCl - is unstable at high temperature (above 1200°C).

rearranging,

A=hc/E

"Black Body" Emission

The presence of solid particles in a pyrotechnic flame can lead to

-7

a substantial loss of color purity due to a complex process known

= 5.89 X 10

meters

as "black body radiation." Solid particles, heated to high tem-

= 589 nm (where 1 nm = 10 -9 meters)

perature, radiate a continuous spectrum of light, much of it in the visible region - with the intensity exponentially increasing Light of wavelength 589 nanometers falls in the yellow portion of with temperature. If you are attempting to produce white light the visible region of the electromagnetic spectrum. The charac-

(which is a combination of all wavelengths in the visible region), teristic yellow glow of sodium vapor lamps used to illuminate many this incandescent phenomenon is desirable.

highways results from this particular emission.

Magnesium metal is found in most "white light" formulas. In To produce this type of atomic emission in a pyrotechnic sys-an oxidizing flame, the metal is converted to the high-melting tem, one must produce sufficient heat to generate atomic vapor magnesium oxide, MgO, an excellent white-light emitter.

Also,

in the flame, and then excite the atoms from the ground to vari-the high heat output of magnesium-containing compositions aids ous possible excited electronic states. Emission intensity will in-in achieving high flame temperatures.

Aluminum metal is also

crease as the flame temperature increases, as more and more atoms commonly used for light production; other metals, including ti-are vaporized and excited. Return of the atoms to their ground tanium and zirconium, are also good white-light sources.

state produces the light emission. A pattern of wavelengths, The development of color and light-producing compositions will known as an atomic spectrum, is produced by each element. This be considered in more detail in Chapter 7.

pattern - a series of lines - corresponds to the various electronic

Chemistry of Pyrotechnics

REFERENCES

R. C. Weast (Ed.), CRC Handbook of Chemistry and Physics, 63rd Ed., CRC Press, Inc. , Boca Raton, Florida, 1982.

A. A. Shidlovskiy, Principles of Pyrotechnics, 3rd Edition,

Moscow, 1964. (Translated as Report FTD-HC-23-1704-74

by Foreign Technology Division, Wright-Patterson Air Force Base, Ohio, 1974.)

L. Pytlewski, "The Unstable Chemistry of Nitrogen," presented at Pyrotechnics and Explosives Seminar P-81, Franklin Research Center, Philadelphia, Penna. , August, 1981.

U.S. Army Material Command, Engineering Design Handbook, Military Pyrotechnic Series, Part Three, "Properties of Materials Used in Pyrotechnic Compositions," Washington, D .C . , 1963 (AMC Pamphlet 706-187).

T. L. Davis, The Chemistry of Powder and Explosives, John Wiley & Sons, Inc., New York, 1941.

U.S. Army Material Command, Engineering Design Handbook, Military Pyrotechnic Series, Part One, "Theory and Application, Washington, D.C., 1967 (AMC Pamphlet 706-185).

J. H. McLain, Pyrotechnics from the Viewpoint of Solid State Chemistry, The Franklin Institute Press, Philadelphia, Penna., 1980.

R. L. Tuve, Principles of Fire Protection Chemistry, National Fire Protection Assn., Boston, Mass., 1976.

W. J. Moore, Basic Physical Chemistry, Prentice Hall, Englewood Cliffs, NJ, 1983.

10.

W. W. Wendlandt, Thermal Methods of Analysis, Inter-science, New York, 1964.

A "pinwheel" set piece, reflected over water. Cardboard tubes are loaded with spark-producing pyrotechnic composition.

The "pin-

wheel," attached to a pole, revolves about its axis as hot gases are vented out the end of a "driver" tube to provide thrust. Sparks are produced by the burning of large particles of charcoal or aluminum.

(Zambelli Internationale)

3COMPONENTS OF

HIGH-ENERGY MIXTURES

I NTRODUCTION

Compounds containing both a readily-oxidizable and a readily-reducible component within one molecule are uncommon. Such species tend to have explosive properties.

A molecule or ionic

compound containing an internal oxidizer/reducer pair is inherently the most intimately-mixed high energy material that can be prepared. The mixing is achieved at the molecular (or ionic) level, and no migration or diffusion is required to bring the electron donor and electron acceptor together.

The electron

transfer reaction is expected to be rapid (even violent) in such species, upon application of the necessary activation energy to a small portion of the composition. A variety of compounds possessing this intramolecular reaction capability are shown in Table 3. 1.

The output from the exothermic decomposition of these compounds is typically heat, gas, and shock. Many of these materials detonate - a property quite uncommon with mixtures, where the degree of homogeneity is considerably less.The high-energy chemist can greatly expand his repertoire of materials by preparing mixtures, combining an oxidizing material with a fuel to produce the exact heat output and burning rate needed for a particular application. Bright light, colors, and smoke can also be produced using such mixtures, adding additional dimensions to the uses of high-energy materials.

For these effects to be achieved, it is critical that the mixture 49

Chemistry o f Pyrotechnics

Components of High-Energy Mixtures

TABLE 3.1

Compounds Containing Intramolecular

OXIDIZING AGENTS

Oxidation -Reduction Capability

Requirements

Compound

Formula

Oxidizing agents are usually oxygen-rich ionic solids that decompose at moderate-to-high temperatures, liberating oxygen gas.

Ammonium nitrate

NH,,NO 3

These materials must be readily available in pure form, in the Ammonium perchlorate

NH,,ClO,,

proper particle size, at reasonable cost. They should give a neutral reaction when wet, be stable over a wide temperature Lead azide

Pb(N,),

range (at least up to 100°C), and yet readily decompose to re-Trinitrotoluene (TNT)

C 7H SN 306

lease oxygen at higher temperatures. For the pyrotechnic chemist's use, acceptable species include a variety of negative ions Nitroglycerine (NG)

C 3H SN 3O 9

(anions), usually containing high-energy Cl-O or N-O bonds: Mercury fulminate

Hg(ONC) 2

NO3

nitrate ion

C103

chlorate ion

Note: These compounds readily undergo explosive C10

perchlorate ion

Cr0 4

chromate ion

decomposition when sufficient ignition stimulus is 0=

oxide ion

2 0 7

dichromate ion

applied. A shock stimulus is frequently needed to activate the nonionic organic molecules (e.g., TNT) ; The positive ions used to combine with these anions must form these compounds will frequently merely burn if a compounds meeting several restrictions [1]

flame is applied.

1. The oxidizer must be quite low in hygroscopicity, or the tendency to acquire moisture from the atmosphere. Water can cause a variety of problems in pyrotechnic mixtures, and materials that readily pick up water may not be used.

burn rather than explode. Burning behavior is dependent upon Sodium compounds in general are quite hygroscopic (e.g., a number of factors, and the pyrotechnist must carefully con-sodium nitrate - NaNO 3) and thus they are rarely em-trol these variables to obtain the desired performance.

ployed. Potassium salts tend to be much better, and are Pyrotechnic mixtures "burn," but it must be remembered that commonly used in pyrotechnics. Hygroscopicity tends to these materials supply their own oxygen for combustion, through parallel water solubility, and solubility data can be used the thermal decomposition of an oxygen-rich material such as po-to anticipate possible moisture-attracting problems. The tassium chlorate

water solubility of the common oxidizers can be found in Table 3.2. However, it should be mentioned that large heat

2 KC1O3

2 KCI + 3 0

(3.1)

quantities of sodium nitrate are used by the military in 2

combination with magnesium metal for white light produc-Thus, a pyrotechnic fire can not be suffocated - no air is needed tion. Here, strict humidity control is required through-for these mixtures to vigorously burn. In fact, confinement can out the manufacturing process to avoid moisture uptake, accelerate the burning of a pyrotechnic composition by producing and the finished items must be sealed to prevent water an increase in pressure, possibly leading to an explosion. Ade-from being picked up during storage.

quate venting is quite important in keeping a pyrotechnic fire 2. The oxidizer's positive ion (cation) must not adversely af-from developing into a serious explosion.

fect the desired flame color. Sodium, for example, is an A variety of ingredients, each serving one or more purposes, intense emitter of yellow light, and its presence can ruin can be used to create an effective composition.

attempts to generate red, green, and blue flames.

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

TABLE 3.2

The Common Oxidizers and Their Properties

Water solu-

Heat of

Grams of oxy- Weight of oxidizer

bility,

decompo- formation, gen released required to evolve one gram of

Formula

Melting point,

grams /100

sition,

kcal /

per gram of

ml @ 20°Ca kcal/mole

molea

oxidizer

oxygen

Compound

Formula

weight

oca

. 60 (total 0)

Ammonium nitrate

NH,,N0 3

80.0

170

118 (0°C)

-87.4

Approx. 0.28

Approx. 3.5

Ammonium perchlorate

NH,,C1O,,

117.5

Decomposes

37.2 c

-70.6

. 32

3.12

Barium chlorate

Ba(C10 3 ) 2 • H 20

322. 3

414

27 (15 0 )

-28b

-184.4

. 095

10.6

Barium chromate

B aCrO,,

253.3

Decomposes

. 0003 (16°)

- 345.6

8.7

+104b

-237.1

. 31

3.27

Barium nitrate

Ba(N03)2

261.4

592

Very slight

+17b

-151.6

. 09

10.6

Barium peroxide

Ba0

169.3

450

. 30

3.33

Iron oxide (red)

Fe 20 3

159.7

1565

Insol.

-197.0

. 28

3.62

Iron oxide (black)

Fe 3 0 y

231.6

1594

Insol.

+266 b

-267.3

Insol.

-218

. 074

13.5

Lead chromate

Pb C r0,,

323.2

844

Insol.

-66.3

. 13 (total 0)

7.48

Lead dioxide

PbO 2

239.2

290 (decomposes)

(lead peroxide)

. 072 (total 0)

14.0

Lead oxide

PbO

223.2

886

. 0017

-51.5

(litharge)

Insol.

-171.7

. 093 (total 0)

10.7

Lead tetroxide

Pb 3 0

685.6

500 (decomposes)

(red lead)

7.1

-10.6c

-95.1

. 39

2.55

Potassium chlorate

KC1O 3

122.6

356

31.60

+75.5b

-118.2

. 40

2.53

Potassium nitrate

KNO 3

101.1

334

1.7c

-0.68c

-103.4

. 46

2.17

Potassium per-

K C 10

138.6

610

chlorate

92.1 (25 ° ) e

+60.5 b

-111.8

. 47

2.13

Sodium nitrate

NaN0 3

85.0

307

70.9 (18°)

+92c

-233.8

. 38

2.63

Strontium nitrate

Sr(N 0 3)2

211.6

570

a Reference 4.

b Reference 1.

cReference 2.

5 4

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

3. The alkali metals (Li, Na, K) and alkaline earth metals additional details on the properties of these and other pyrotech-

(Ca, Sr, and Ba) are preferred for the positive ion.

nic materials [1, 2, 3].

These species are poor electron acceptors (and con-versely, the metals are good electron donors), and they will not react with active metal fuels such as Mg and Al.

Potassium Nitrate (KNO 3 )

If easily reducible metal ions such as lead (Pb +2) and The oldest solid oxidizer used in high-energy mixtures, potassium copper (Cu +2) are present in oxidizers, there is a strong nitrate (saltpeter) remains a widely-used ingredient well into the possibility that a reaction such as

20th century. Its advantages are ready availability at reasonable Cu(N0

cost, low hygroscopicity, and the relative ease of ignition of many 3 ) 2 + Mg -> Cu + Mg(NO 3 ) 2

mixtures prepared using it. The ignitibility is related to the low will occur, especially under moist conditions. The pyro-

(334°C) melting point of saltpeter. It has a high (39.6%) active technic performance will be greatly diminished, and spon-oxygen content, decomposing at high temperature according to taneous ignition might occur.

the equation

4. The compound must have an acceptable heat of decomposition. A value that is too exothermic will produce explo-2KNO 3 + K 2O+N 2 +2.502

sive or highly sensitive mixtures, while a value that is This is a strongly endothermic reaction, with a AH value of +75.5

too endothermic will cause ignition difficulties as well as kcal/mole of KNO 3 , meaning high energy-output fuels must be poor propagation of burning.

used with saltpeter to achieve rapid burning rates. When mixed 5. The compound should have as high an active oxygen con-with a simple organic fuel such as lactose, potassium nitrate may tent as possible. Light cations (Na+, K+, NH,,+) are de-stop at the potassium nitrite (KNO 2 ) stage in its decomposition [2].

sirable while heavy cations (Pb +2 , Ba +2) should be avoided if possible. Oxygen-rich anions, of course, are preferred.

KNO 3 } KNO2 + 1/2 0 2

6. Finally, all materials used in high-energy compositions With good fuels (charcoal or active metals) , potassium nitrate will should be low in toxicity, and yield low-toxicity reaction burn well. Its use in colored flame compositions is limited, pri-products.

marily due to low reaction temperatures. Magnesium may be added to these mixtures to raise the temperature (and hence the light in-In addition to ionic solids, covalent molecules containing halo-tensity), but the color value is diminished by "black body" emis-gen atoms (primarily F and Cl) can function as "oxidizers" in sion from solid MgO.

pyrotechnic compositions, especially with active metal fuels. Ex-Potassium nitrate has the additional property of not undergoing amples of this are the use of hexachloroethane (C

an explosion by itself, even when very strong initiating modes are 2 C1 6 ) with zinc

metal in white smoke compositions,

used [2].

3 Zn + C2C1 6 -> 3 ZnC12 + 2 C

Potassium Chlorate (KCIO 3)

and the use of Teflon with magnesium metal in heat-producing mixtures,

One of the very best, and certainly the most controversial, of the common oxidizers is potassium chlorate, KC1O 3 . It is a white, (C 2F,,) n + 2n Mg -} 2n C + 2n MgF 2 + heat crystalline material of low hygroscopicity, with 39.2% oxygen by In both of these examples, the metal has been "oxidized" - has weight. It is prepared by electrolysis from the chloride salt.

lost electrons and increased in oxidation number -- while the car-Potassium chlorate was used in the first successful colored-bon atoms have gained electrons and been "reduced."

flame compositions in the mid-1800's and it remains in wide use Table 3.2 lists some of the common oxidizers together with a today in colored smoke, firecrackers, toy pistol caps, matches, variety of their properties.

and color-producing fireworks.

Several oxidizers are so widely used that they merit special However, potassium chlorate has been involved in a large consideration. A few excellent books are available that provide percentage of the serious accidents at fireworks manufacturing

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

plants, and it must be treated with great care if it is used at all.

TABLE 3.3 Ignition Temperatures of Potassium Other oxidizers are strongly recommended over this material, if Chlorate/Fuel Mixtures

one can be found that will produce the desired pyrotechnic ef-Ignition temperature of

fect.Potassium chlorate compositions are quite prone to accidental stoichiometric mixture,

ignition, especially if sulfur is also present. Chlorate /phosphor-Fuel

us mixtures are so reactive that they can only be worked with when quite wet. The high hazard of KC1O

Lactose, C1211 22011

195

3 mixtures was grad-

ually recognized in the late 19th century, and England banned Sulfur

220

all chlorate /sulfur compositions in 1894. United States factories have greatly reduced their use of potassium chlorate as well, Shellac

250

replacing it with the less-sensitive potassium perchlorate in Charcoal

335

many formulas. The Chinese, however, continue to use potassium chlorate in firecracker and color compositions. Details on Magnesium powder

540

their safety record are not available, although several accidents Aluminum powder

785

are known to have occurred at their plants in recent years.

Several factors contribute to the instability of potassium chlor-Graphite

890

ate-containing compositions. The first is the low (356°C) melting point and low decomposition temperature of the oxidizer. Soon aReference 1.

after melting, KC1O 3 decomposes according to equation 3.1.

2 KC10

} 2 KC1 + 3 02

(3.1)

This reaction is quite vigorous, and becomes violent at temperatures above 500°C [2]. The actual decomposition mechanism may be more complex than equation 3.1 suggests. Intermediate temperatures are observed for most such compositions. Higher formation of potassium perchlorate has been reported at tempera-ignition temperatures are found for KC1O 3 /metal mixtures, at-tures just above the melting point, with the perchlorate then de-tributable to the higher melting points and rigid crystalline lat-composing to yield potassium chloride and oxygen [5].

tices of these metallic fuels. However, these mixtures can be quite sensitive to ignition because of their substantial heat out-4 KC1O 3 -} 3 KC10 4 + KCl

put, and should be regarded as quite hazardous. Ignition tem-3 KC10,, - 3 KC1

+ 60,

peratures for some KC1O 3 mixtures are given in Table 3.3. Note: Ignition temperatures are quite dependent upon the experimental net: 4 KC1O 3 ; 4 KCl + 6 0 2

conditions; a range of +/-50 0 may be observed, depending on The decomposition reaction of potassium chlorate is rare among sample size, heating rate, degree of confinement, etc. [6].

the common oxidizers because it is exothermic, with a heat of re-Mixtures containing potassium chlorate can be quite suscep-action value of approximately -10.6 kcal/mole [ 2]. While most tible to the presence of a variety of chemical species. Acids other oxidizers require a net heat input for their decomposition, can have a dramatic effect - the addition of a drop of concen-potassium chlorate dissociates into KC1 and 0

trated sulfuric acid (H 2SO 4) to most KCIO 3 /fuel mixtures results 2 with the liberation

in immediate inflammation of the composition. This dramatic re-of heat. This heat output can lead to rate acceleration, and allows the ignition of potassium chlorate-containing compositions activity has been attributed to the formation of chlorine dioxide (C10

with a minimum of external energy input (ignition stimulus).

2 ) gas, a powerful oxidizer [5]. The presence of basic Potassium chlorate is particularly sensitive when mixed with

"neutralizers" such as magnesium carbonate and sodium bicarbonate in KC1O

sulfur, a low-melting (119°C) fuel. It is also sensitive when 3 mixtures can greatly lower the sensitivity of combined with low-melting organic compounds, and low ignition these compositions to trace amounts of acidic impurities.

Ah' AL_

5 8

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

The ability of a variety of metal oxides -- most notably man-through an endothermic decomposition, in the flame, of the ganese dioxide, Mn0 2 - to catalyze the thermal decomposition of type

potassium chlorate into potassium chloride and oxygen has been known for years. Little use is made of this behavior in pyro-heat

MgCO3

MgO + CO2

technics, however, because KC10 3 is almost too reactive in its normal state and ways are not needed to enhance its reactivity.

Colored smoke mixtures also contain either sulfur or a carbohy-Materials and methods to retard its decomposition are desired drate as the fuel, and a volatile organic dye that sublimes from instead. However, knowledge of the ability of many materials to the reaction mixture to produce the colored smoke. These com-accelerate the decomposition of KC10

positions contain a large excess of potential fuel, and their ex-3 suggests that impurities

could be quite an important factor in determining the reactivity plosive properties are greatly diminished as a result. Smoke and ignition temperature of chlorate-containing mixtures. It is mixtures must react with low flame temperatures (500°C or less) vitally important that the KCIO

or the complex dye molecules will decompose, producing black 3 used in pyrotechnic manufacturing operations be of the highest possible purity, and that all soot instead of a brilliantly colored smoke. Potassium chlorate possible precautions be taken in storage and handling to pre-is far and away the best oxidizer for use in these compositions.

vent contamination of the material.

Potassium chlorate is truly a unique material. Shimizu has McLain has reported that potassium chlorate containing 2.8

stated that no other oxidizer can surpass it for burning speed, mole% copper chlorate as an intentionally-added impurity (or ease of ignition, or noise production using a minimum quantity

"dopant") reacted explosively with sulfur at room temperature of composition [2]. It is also among the very best oxidizers for

[7]! A pressed mixture of potassium chlorate with realgar (ar-producing colored flames, with ammonium perchlorate as its senic sulfide, As

closest rival. Chlorate-containing compositions can be prepared 2S2) has also been reported to ignite at room temperature [2].

that will ignite and propagate at low flame temperatures - a Ammonium chlorate, NH,,C10

property invaluable in colored smoke mixtures. By altering the 3 , is an extremely unstable compound that decomposes violently at temperatures well below 100 0 C.

fuel and the fuel/oxidizer ratio, much higher flame temperatures If a mixture containing both potassium chlorate and an ammonium can be achieved for use in colored flame formulations. KC10 3 is salt is prepared, there is a good possibility that an exchange re-a versatile material, but the inherent danger associated with it action will occur -- especially in the presence of moisture - to requires that alternate oxidizers be employed wherever possible.

form some of the ammonium chlorate

It is just too unstable and unpredictable to be safely used by the pyrotechnician in anything but colored smoke compositions, and NH,,X + KC1O3 HZO NH4C103 + KX

even here coolants and considerable care are required!

(X = C1- , N0 -3 , C1O,, , etc.)

Potassium Perchlorate (KCIO,,)

If this reaction occurs, the chance of spontaneous ignition of the mixture is likely. Therefore, any composition containing both a This material has gradually replaced potassium chlorate (KC10 3 ) chlorate salt and an ammonium salt must be considered extremely as the principal oxidizer in civilian pyrotechnics. Its safety rec-hazardous. The shipping regulations of the United States De-ord is far superior to that of potassium chlorate, although cau-partment of Transportation classify any such mixtures as "for-tion - including static protection - must still be used. Perchlor-bidden explosives" because of their instability [8]. However, ate mixtures, especially with a metal fuel such as aluminum, can compositions consisting of potassium chlorate, ammonium chlor-have explosive properties, especially when present in bulk quan-ide, and organic fuels have been used, reportedly safely, for tities and when confined.

white smoke production [1].

Potassium perchlorate is a white, non-hygroscopic crystalline Colored smoke compositions are a major user of potassium material with a melting point of 6101C, considerably higher than chlorate, and the safety record of these mixtures is excellent.

the 356°C melting point of KC10 3 . It undergoes decomposition at A neutralizer (e.g., MgCO

high temperature

3 or NaHCO 3 ) is typically added for

storage stability, as well as to lower the reaction temperature heat

KC1O,,

KC1 + 2 0 2

Chemistry o f Pyrotechnics

Components of High-Energy Mixtures

forming potassium chloride and oxygen gas. This reaction has taken to keep mixtures dry. The hygroscopicity problem can be a slightly exothermic value of -0.68 kcal/mole [2] and produces substantial if a given composition also contains potassium nitrate, substantial oxygen.

The active oxygen content of KC1O,, -

or even comes in contact with a potassium nitrate-containing mix-46.2% - is one of the highest available to the pyrotechnician.

ture.

Here, the reaction

Because of its higher melting point and less-exothermic de-H?O

composition, potassium perchlorate produces mixtures that are NH L C1O k + KNO3

KC1O y + NH„NO 3

less sensitive to heat, friction, and impact than those made can occur, especially in the presence of moisture. The exchange with KC1O 3 [2].

Potassium perchlorate can be used to pro-

product, ammonium nitrate (NH,,N0 3 ) is very hygroscopic, and duce colored flames (such as red when combined with stron-ignition problems may well develop [2]. Also, ammonium per-tium nitrate), noise (with aluminum, in "flash and sound"

chlorate should not be used in combination with a chlorate-con-mixtures), and light (in photoflash mixtures with magnesium).

taining compound, due to the possible formation of unstable ammonium chlorate in the presence of moisture.

Ammonium Perchlorate (NH,,CIO,,)

Magnesium metal should also be avoided in ammonium perchlorate compositions.

Here, the reaction

The "newest" oxidizer to appear in pyrotechnics, ammonium perchlorate has found considerable use in modern solid-fuel rocket 2 NH,,C10,, + Mg } 2 NH 3 + Mg(Cl0 4 ) 2 + H 2 + heat propellants and in the fireworks industry.

The space shuttle

can occur in the presence of moisture. Spontaneous ignition may alone uses approximately two million pounds of solid fuel per occur if the heat buildup is substantial.

launch; the mixture is 70% ammonium perchlorate, 16% aluminum Under severe initiation conditions, ammonium perchlorate can metal, and 14% organic polymer.

be made to explode by itself [10] . Mixtures of ammonium per-Ammonium perchlorate undergoes a complex chemical reac-chlorate with sulfur and antimony sulfide are reported to be con-tion on heating, with decomposition occurring over a wide range, siderably more shock sensitive than comparable KC1O 3 composi-beginning near 200°C.

Decomposition occurs prior to melting,

tions [2].

Ammonium perchlorate can be used to produce excel-so a liquid state is not produced - the solid starting material lent colors, with little solid residue, but care must be exercised goes directly to gaseous decomposition products.

The decom-

at all times with this oxidizer. The explosive properties of this position reaction is reported by Shimizu [2] to be material suggest that minimum amounts of bulk composition should be prepared at one time, and large quantities should not be stored 2 NH,,C104 heat N2 +3H 2 0+2HC1+2.50 2

at manufacturing sites.

This equation corresponds to the evolution of 80 grams (2.5

moles) of oxygen gas per 2 moles (235 grams) of NH I C1O,, , Strontium Nitrate [Sr(NO3)2]

giving an "active oxygen" content of 34% (versus 39.2% for KC1O

This material is rarely used as the only oxidizer in a composition, 3

and 46.2% for KC10,,).

The decomposition reaction,

above 350 1 C, is reported to be considerably more complex [9].

but is commonly combined with potassium perchlorate in red flame mixtures. It is a white crystalline solid with a melting point of heat,

10 NH,,C10,,

2.5 C1

approximately 570°C. It is somewhat hygroscopic, so moisture 2

+ 2 N 2 0 + 2.5 NOC1 + HC10 4

should be avoided when using this material.

+1.5HC1+18.75H 2 O+1.75N 2 +6.3802

Near its melting point, strontium nitrate decomposes accord-Mixtures of ammonium perchlorate with fuels can produce high ing to

temperatures when ignited, and the hydrogen chloride (HCl) lib-Sr(NO 3 ) 2 -} SrO + NO + NO 2 + 0 2

erated during the reaction can aid in the production of colors.

These two factors make ammonium perchlorate a good oxidizer Strontium nitrite - Sr(N0 2 ) 2 - is formed as an intermediate in for colored flame compositions (see Chapter 7).

this decomposition reaction, and a substantial quantity of the ni-Ammonium perchlorate is more hygroscopic than potassium trite can be found in the ash of low flame temperature mixtures nitrate or potassium chlorate, and some precautions should be

[2].

At higher reaction temperatures, the decomposition is

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

Sr(NO 3 ) 2 -> SrO + N 2 + 2.5 0 2

which later melts at 41_4 0 C.

The thermal decomposition of barium

This is a strongly endothermic reaction, with a heat of reaction chlorate is strongly exothermic (-28 kcal/mole). This value, con-of +92 kcal, and corresponds to an active oxygen content of siderably greater than that of potassium chlorate, causes barium 37.7%.

Little ash is produced by this high-temperature process, chlorate mixtures to be very sensitive to friction, heat, and other which occurs in mixtures containing magnesium or other "hot"

ignition stimuli.

fuels

Iron oxide (hematite, Fe 2 0 3 ) is used in certain mixtures where a high ignition temperature and a substantial quantity of molten slag (and lack of gaseous product) are desired. The thermite re-Barium Nitrate [Ba(N03)2]

action ,

Barium nitrate is a white, crystalline, non-hygroscopic material Fe2O3+2Al- A1

with a melting point of approximately 592°C. It is commonly used 2O 3 +2Fe

as the principal oxidizer in green flame compositions, gold spark-is an example of this type of reaction, and can be used to do pyro-lers, and in photoflash mixtures in combination with potassium technic welding.

The melting point of Fe 20 3 is 1565°C, and the pert hlorate .

ignition temperature of thermite mix is above 800 0 C.

A reaction

At high reaction temperatures, barium nitrate decomposes ac-temperature of approximately 2400°C is reached, and 950 calories cording to

of heat is evolved per gram of composition [2, 51.

Other oxidizers, including barium chromate (BaCrO,,), lead Ba(NO 3 ) 2 -+ BaO + N 2 + 2.5 0 2

chromate (PbCrO 4) , sodium nitrate (NaNO 3), lead dioxide (Pb0 2) , This reaction corresponds to 30.6% available oxygen. At lower and barium peroxide (Ba0 2) will also be encountered in subse-reaction temperatures, barium nitrate produces nitrogen oxides quent chapters. Bear in mind that reactivity and ease of igni-

(NO and NO

tion are often related to the melting point of the oxidizer, and the 2 ) instead of nitrogen gas, as does strontium nitrate 21.

volatility of the reaction products determines the amount of gas Mixtures containing barium nitrate as the sole oxidizer are that will be formed from a given oxidizer /fuel combination. Table typically characterized by high ignition temperatures, relative 3.2 contains the physical and chemical properties of the common to potassium nitrate and potassium chlorate compositions. The oxidizers, and Table 5.8 lists the melting and boiling points of higher melting point of barium nitrate is responsible for these some of the common reaction products.

higher ignition values.

Shidlovskiy has pointed out that metal-fluorine compounds should also have good oxidizer capability. For example, the reaction

Other Oxidizers

FeF

A variety of other oxidizers are also occasionally used in high-3 + Al } A1F 3 + Fe

energy mixtures, generally with a specific purpose in mind.

is quite exothermic (z~H = -70 kcal). However, the lack of stable, Barium chlorate - Ba(C10 3 ) 2 - for example is used in some economical metal fluorides of the proper reactivity has limited re-green flame compositions. These mixtures can be very sensi-search in this direction [ 1] .

tive, however, and great care must be used during mixing, loading, and storing. Barium chlorate can be used to produce a beautiful green flame, though.

FUELS

Barium chlorate is interesting because it exists as a hydrate Requirements

when crystallized from a water solution. It has the formula Ba(C10

In addition to an oxidizer, pyrotechnic mixtures will also contain 3 ) 2 • H 2 O.

Water molecules are found in the crystalline lattice in a one-to-one ratio with barium ions. The molecular a good fuel - or electron donor - that reacts with the liberated weight of the hydrate is 322.3 (Ba + 2

+ H 2O), so the wa-

oxygen to produce an oxidized product plus heat. This heat will CIO 3

ter must be included in stoichiometry calculations. On heating, enable the high-energy chemist to produce any of a variety of the water is driven off at 120°C, producing anhydrous Ba(C103)2, possible effects - color, motion, light, smoke, or noise.

6 4

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

The desired pyrotechnic effect must be carefully considered A good fuel will react with oxygen (or a halogen like fluorine when a fuel is selected to pair with an oxidizer for a high-en-or chlorine) to form a stable compound, and substantial heat will ergy mixture. Both the flame temperature that will be produced be evolved. The considerable strength of the metal-oxygen and and the nature of the reaction products are important factors.

metal-halogen bonds in the reaction products accounts for the The requirements for some of the major pyrotechnic categories excellent fuel properties of many of the metallic elements.

are

A variety of materials can be used, and the choice of material will depend on a variety of factors - the amount of heat output required, rate of heat release needed, cost of the materials, sta-1. Propellants: A combination producing high temperature, a bility of the fuel and fuel /oxidizer pair, and amount of gaseous large volume of low molecular weight gas, and a rapid burn-product desired. Fuels can be divided into three main categor-ning rate is needed. Charcoal and organic compounds are ies. metals, non-metallic elements, and organic compounds.

often found in these compositions because of the gaseous products formed upon their combustion.

2. Illuminating compositions: A high reaction temperature is Metals

mandatory to achieve intense light emission, as is the pres-A good metallic fuel resists air oxidation and moisture, has a high ence in the flame of strong light-emitting species. Magne-heat output per gram, and is obtainable at moderate cost in fine sium is commonly found in such mixtures due to its good particle sizes. Aluminum and magnesium are the most widely used heat output. The production of incandescent magnesium materials. Titanium, zirconium, and tungsten are also used, es-oxide particles in the flame aids in achieving good light in-pecially in military applications.

tensity. Atomic sodium, present in vapor form in a flame, The alkali and alkaline earth metals - such as sodium, potas-is a very strong light emitter, and sodium emission domi-sium, barium, and calcium -- would make excellent high-energy nates the light output from the widely used sodium nitrate/

fuels, but, except for magnesium, they are too reactive with magnesium compositions.

moisture and atmospheric oxygen. Sodium metal, for example, 3. Colored flame compositions : A high reaction temperature reacts violently with water and must be stored in an inert or-produces maximum light intensity, but color quality depends ganic liquid, such as xylene, to minimize decomposition.

upon having the proper emitters present in the flame, with A metal can initially be screened for pyrotechnic possibilities a minimum of solid and liquid particles present that are by an examination of its standard reduction potential (Table 2. 5).

emitting a broad spectrum of "white" light. Magnesium is A readily oxidizable material will have a large, negative value, sometimes added to colored flame mixtures to obtain higher meaning it possesses little tendency to gain electrons and a sig-intensity, but the color quality may suffer due to broad nificant tendency to lose them. Good metallic fuels will also be emission from MgO particles. Organic fuels (red gum, reasonably lightweight, producing high calories/gram values dextrine, etc.) are found in most color mixtures used in when oxidized. Table 3.4 lists some of the common metallic fuels the fireworks industry.

and their properties.

4. Colored smoke compositions: Gas evolution is needed to disperse the smoke particles. High temperatures are not desirable here because decomposition of the organic dye Aluminum (Al)

molecules will occur. Metals are not found in these mix-The most widely used metallic fuel is probably aluminum, with tures. Low heat fuels such as sulfur and sugars are com-magnesium running a close second. Aluminum is reasonable in monly employed.

cost, lightweight, stable in storage, available in a variety of 5. Ignition compositions: Hot solid or liquid particles are de-particle shapes and sizes, and can be used to achieve a variety sirable in igniter and first-fire compositions to insure the of effects.

transfer of sufficient heat to ignite the main composition.

Aluminum has a melting point of 660°C and a boiling point of Fuels producing mainly gaseous products are not com-approximately 2500°C. Its heat of combustion is 7.4 kcal/gram.

monly used.

Chemistry

Components o f High-Energy Mixtures

of Pyrotechnics

Aluminum is available in either "flake" or "atomized" form.

The "atomized" variety consists of spheroidal particles. Spheres yield the minimum surface area (and hence minimum reactivity) for a given particle size, but this form will be the most reproducible in performance from batch to batch. Atomized aluminum, rather than the more reactive flake material, is used by the military for heat and light-producing compositions because the variation in performance from shipment to shipment is usually less.

Large flakes, called "flitter" aluminum, are widely used by the fireworks industry to produce bright white sparks. A special

"pyro" grade of aluminum is also available from some suppliers.

This is a dark gray powder consisting of small particle sizes and high surface area and it is extremely reactive. It is used to produce explosive mixtures for fireworks, and combinations of oxidizers with this "pyro" aluminum should only be prepared by skilled personnel, and only made in small batches. Their explosive power can be substantial, and they can be quite sensitive to ignition.

Aluminum surfaces are readily oxidized by the oxygen in air, and a tight surface coating of aluminum oxide (A120 3) is formed that protects the inner metal from further oxidation. Hence, aluminum powder can be stored for extended periods with little loss of reactivity due to air oxidation. Metals that form a loose oxide coating on exposure to air - iron, for example - are not provided this surface protection, and extensive decomposition can occur during storage unless appropriate precautions are taken.

Compositions made with aluminum tend to be quite stable.

However, moisture must be excluded if the mixture also contains a nitrate oxidizer. Otherwise, a reaction of the type 3KNO 3 +8Al+12H20-> 3KA1O2 +5A1(OH) 3 +3NH 3

can occur, evolving heat and ammonia gas. This reaction is accelerated by the alkaline medium generated as the reaction proceeds, and autoignition is possible in a confined situation. A small quantity of a weak acid such as boric acid (H 3B03) can effectively retard this decomposition by neutralizing the alkaline products and maintaining a weakly acidic environment. The hygroscopicity of the oxidizer is also important in this decomposition process. Sodium nitrate and aluminum can not be used together, due to the high moisture affinity of NaNO3 , unless the aluminum powder is coated with a protective layer of wax or similar material. Alternatively, the product can be sealed in a moisture-proof packaging to exclude any water [1]. Potassium nitrate/

aluminum compositions must be kept quite dry in storage to avoid

All

Chemistry o f Pyrotechnics

Components o f High-Energy Mixtures

decomposition problems, but mixtures of aluminum and non-hygro-Cu +2 + Mg _

+ Mg+

scopic barium nitrate can be stored with a minimum of precautions, This process becomes much more probable if a composition is mois-as long as the composition does not actually get wet. Mixtures of magnesium metal with nitrate salts do not have this alkaline-cata-tened, again pointing out the variety of problems that can be created if water is added to a magnesium-containing mixture. The lyzed decomposition problem.

A magnesium hydroxide (Mg(OH) 2 ]

coating on the metal surface apparently protects it from further standard potential for the Cu +2 /Mg system is +2.72 volts, indicating a very spontaneous process. Therefore, Cu +2 , Pb +2 , and reaction.

This protection is not provided to aluminum metal by

other readily-reducible metal ions must not be used in magnesium-the alkaline soluble aluminum hydroxide, Al(OH) 3 .

containing compositions.

Magnesium (Mg)

"Magnalium" (Magnesium-Aluminum Alloy) Magnesium is a very reactive metal and makes an excellent fuel A material finding increasing popularity in pyrotechnics is the under the proper conditions. It is oxidized by moist air to form 50/50 alloy of magnesium and aluminum, termed "magnalium."

magnesium hydroxide, Mg(OH) 2 , and it readily reacts with all Shimizu reports that this material is a solid solution of Al acids, including weak species such as vinegar (5% acetic acid) 3 Mg 2 in

and boric acid. The reactions of magnesium with water and an Al 2 Mg 3 , with a melting point of 460°C [2]. The alloy is considerably more stable than aluminum metal when combined with ni-acid (HX) are shown below:

trate salts, and reacts much more slowly than magnesium metal Water:

Mg + 2 H

+ H

2 O } Mg(OH) 2

with weak acids. It therefore offers stability advantages over Acids (HX): Mg + 2 HX ; MgX

both of its component materials.

2 + H 2 (X = Cl, NO 3 , etc.)

The Chinese make wide use of magnalium in fireworks items Even the ammonium ion, NH 4+, is acidic enough to react with to produce attractive white sparks and "crackling" effects.

magnesium metal.

Therefore, ammonium perchlorate and other

Shimizu also reports that a branching spark effect can be pro-ammonium salts should not be used with magnesium unless the duced using magnalium with a black powder-type composition metal surface is coated with linseed oil, paraffin, or a similar

[2] .

material.

Chlorate and perchlorate salts, in the presence of moisture, I ron

will oxidize magnesium metal, destroying any pyrotechnic effect during storage.

Nitrate salts appear to be considerably more Iron, in the form of fine filings, will burn and can be used to stable with magnesium [2].

Again, coating the metal with an

produce attractive gold sparks, such as in the traditional wire organic material - such as paraffin - will increase the storage sparkler.

The small percentage (less than 1%) of carbon in steel lifetime of the composition.

A coating of potassium dichromate

can cause an attractive branching of the sparks due to carbon on the surface of the magnesium has also been recommended to dioxide gas formation as the metal particles burn in air.

aid in stability [21, but the toxicity of this material makes it of Iron filings are quite unstable on storage, however. They questionable value for industrial applications.

readily convert to iron oxide (rust - Fe 2 0 3 ) in moist air, and Magnesium has a heat of combustion of 5. 9 kcal /gram, a melt-filings are usually coated with a paraffin-type material prior to ing point of 649°C, and a low boiling point of 1107°C. This low use in a pyrotechnic mixture.

boiling point allows excess magnesium in a mixture to vaporize and burn with oxygen in the air, providing additional heat (and Other Metals

light) in flare compositions.

No heat absorption is required to

decompose an oxidizer when this excess magnesium reacts with Titanium metal (Ti) offers some attractive properties to the high-

atmospheric oxygen; hence, the extra heat gained by incorpor energy chemist. It is quite stable in the presence of moisture ating the excess magnesium into the mixture is substantial.

and most chemicals, and produces brilliant silver-white spark Magnesium metal is also capable of reacting with other metal and light effects with oxidizers. Lancaster feels that it is a ions in an electron-transfer reaction, such as safer material to use than either magnesium or aluminum, and

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

recommends that it be used in place of iron filings in fireworks

"fountain" items, due to its greater stability [11] . Cost and lack of publicity seem to be the major factors keeping titanium from being a much more widely used fuel.

Zirconium (Zr) is another reactive metal, but its considerable expense is a major problem restricting its wider use in high-energy compositions. It is easily ignited - and therefore quite hazardous - as a fine powder, and must be used with great care.

Non-Metallic Elements

Several readily-oxidized nonmetallic elements have found widespread use in the field of pyrotechnics. The requirements again are stability to air and moisture, good heat-per-gram output, and reasonable cost. Materials in common use include sulfur, boron, silicon, and phosphorus. Their properties are summarized in Table 3.5.

Sulfur

The use of sulfur as a fuel in pyrotechnic compositions dates back over one thousand years, and the material remains a widely-used component in black powder, colored smoke mixtures, and fireworks compositions. For pyrotechnic purposes, the material termed "flour of sulfur" that has been crystallized from molten sulfur is preferred. Sulfur purified by sublimation - termed

"flowers of sulfur" - often contains significant amounts of oxidized, acidic impurities and can be quite hazardous in high-energy mixtures, especially those containing a chlorate oxidizer

[11].

Sulfur has a particularly low (119°C) melting point. It is a rather poor fuel in terms of heat output, but it frequently plays another very important role in pyrotechnic compositions. It can function as a "tinder," or fire starter. Sulfur undergoes exothermic reactions at low temperature with a variety of oxidizers, and this heat output can be used to trigger other, higher-energy reactions with better fuels. Sulfur's low melting point provides a liquid phase, at low temperature, to assist the ignition process. The presence of sulfur, even in small percentage, can dramatically affect the ignitibility and ignition temperature of high-energy mixtures. Sulfur, upon combustion, is converted to sulfur dioxide gas and to sulfate salts (such as potassium sulfate - K 2SOy). Sulfur is also found to act as an oxidizer in some

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

-2

mixtures, winding up as the sulfide ion (S ) in species such as has traditionally been used in toy pistol caps and trick noise-potassium sulfide (K 2S), a detectable component of black powder makers ("party poppers").

combustion residue.

Phosphorus is available in two forms, white (or yellow) and When present in large excess, sulfur may volatilize out of the red. White phosphorus appears to be molecular, with a formula burning mixture as yellowish-white smoke. A 1:1 ratio of po-of P,,. It is a waxy solid with a melting point of 44 0C, and ig-tassium nitrate and sulfur makes a respectable smoke composi-nites spontaneously on exposure to air. It must be kept cool and tion employing this behavior.

is usually stored under water. It is highly toxic in both the solid and vapor form and causes burns on contact with the skin. Its Boron

use in pyrotechnics is limited to incendiary and white smoke compositions. The white smoke consists of the combustion product, Boron is a stable element, and can be oxidized to yield good heat primarily phosphoric acid (H 3PO,,).

output. The low atomic weight of boron (10.8) makes it an ex-Red phosphorus is somewhat more stable, and is a reddish-cellent fuel on a calories/gram basis. Boron has a high melting brown powder with a melting point of approximately 590°C (in point (2300°C), and it can prove hard to ignite when combined the absence of air). In the presence of air, red phosphorus ig-with a high-melting oxidizer. With low-melting oxidizers, such nites near 260°C [2]. Red phosphorus is insoluble in water. It as potassium nitrate, boron ignites more readily yielding good is easily ignited by spark or friction, and is quite hazardous any heat production. The low melting point of the oxide product time it is mixed with oxidizers or flammable materials. Its fumes (B 20 3 ) can interfere with the attainment of high reaction tem-are highly toxic [3].

peratures, however, [1].

Red phosphorus is mixed as a water slurry with potassium Boron is a relatively expensive fuel, but it frequently proves chlorate for use in toy caps and noisemakers. These mixtures acceptable for use on a cost basis because only a small percentage are quite sensitive to friction, impact, and heat, and a large is required (remember, it has a low atomic weight). For example, amount of such mixtures must never be allowed to dry out in the reaction

bulk form. Red phosphorus is also used in white smoke mix-BaCrO,, + B - products (B

tures, and several examples can be found in Chapter 8.

2 0 3 , BaO, Cr 20 3 )

burns well with only 5% by weight boron in the composition [5, 6]. Boron is virtually unknown in the fireworks industry, but Sulfide Compounds

is a widely-used fuel in igniter and delay compositions for mili-Several metallic sulfide compounds have been used as fuels in tary and aerospace applications.

pyrotechnic compositions. Antimony trisulfide, Sb 2S 3 , is a reasonably low-melting material (m.p. 548°C) with a heat of combus-Silicon

tion of approximately 1 kcal/gram. It is easily ignited and can be used to aid in the ignition of more difficult fuels, serving as In many ways similar to boron, silicon is a safe, relatively inex-a "tinder" in the same way that elemental sulfur does. It has pensive fuel used in igniter and delay compositions. It has a high been used in the fireworks industry for white fire compositions melting point (1410°C), and combinations of this material with a and has been used in place of sulfur in "flash and sound" mix-high-melting oxidizer may be difficult to ignite. The oxidation tures with potassium perchlorate and aluminum.

product, silicon dioxide (Si0 2 ) , is high melting and, importantly, Realgar (arsenic disulfide, As 2S2 ) is an orange powder with is environmentally acceptable.

a melting point of 308°C and a boiling point of 565°C [2]. Due to its low boiling point, it has been used in yellow smoke composi-Phosphorus

tions (in spite of its toxicity!) , and has also been used to aid in the ignition of difficult mixtures.

Phosphorus is an example of a material that is too reactive to be The use of all arsenic compounds -- including realgar - is proof any general use as a pyrotechnic fuel, although it is increas-hibited in "common fireworks" (the type purchased by individuals) ingly being employed in military white smoke compositions, and it by regulations of the U. S. Consumer Product Safety Commission [ 121.

Chemistry of Pyrotechnics

a ,

Components of High-Energy Mixtures

Organic Fuels

A variety of organic (carbon-containing) fuels are commonly employed in high-energy compositions. In addition to providing heat, these materials also generate significant gas pressure through the production of carbon dioxide (C0 2) and water vapor in the reaction zone.

The carbon atoms in these molecules are oxidized to carbon dioxide if sufficient oxygen is present. Carbon monoxide (CO) or elemental carbon are produced in an oxygen-deficient atmosphere, and a "sooty" flame is observed if a substantial amount of carbon is generated. The hydrogen present in organic compounds winds up as water molecules. For a fuel of formula C x HyOz , x moles of C0 2 and y/2 moles of water will be produced per mole of fuel that is burned. To completely combust this fuel, x + y/2 moles of oxygen gas (2x + y moles of oxygen atoms) will be required. The amount of oxygen that must be provided by the oxidizer in a high-energy mixture is reduced by the presence of oxygen atoms in the fuel molecule. The balanced equation for the combustion of glucose is shown below C6H 1206 + 6 0 2 - 6 CO2 + 6 H 2O

Only six oxygen molecules are required to oxidize one glucose molecule, due to the presence of six "internal" oxygen atoms in glucose. There are 18 oxygen atoms on both sides of the balanced equation.

A fuel that contains only carbon and hydrogen - termed a hydrocarbon - will require more moles of oxygen for complete combustion than will an equal weight of glucose or other oxygen-containing compound. A greater weight of oxidizer is therefore required per gram of fuel when a hydrocarbon-type material is used.

The grams of oxygen needed to completely combust one gram of a given fuel can be calculated from the balanced chemical equa -

tion. Table 3.6 lists the oxygen requirement for a variety of organic fuels. A sample calculation is shown in Figure 3.1.

To determine the proper ratio of oxidizer to fuel for a stoichio -

metric composition, the grams of oxygen required by a given fuel (Tables 3.4-3.6) must be matched with the grams of oxygen delivered by the desired oxidizer (given in Table 3. 2). For the reaction between potassium chlorate (KC10 3 ) and glucose (C6H1206) , 2.55 grams of KC1O 3 donates 1.00 grams of oxygen, and 0.938

grams of glucose consumes 1.00 grams of oxygen. The proper weight ratio of potassium chlorate to glucose is therefore 2.55: 0.938, and the stoichiometric mixture should be 73.1% KC10 3 and

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

Equation:

C6 H 12 06 + 6 0 2 -> 6 CO 2 + 6 H2O

of crystallization) will evolve less heat than similar, nonhydrated moles

species due to the absorption of heat required to vaporize the wa-grams

1 80

1 92

264

108

ter present in the hydrates.

grams/gram 0

0.938

1.00

Two "hot" organic fuels are shellac and red gum. Shellac, secreted by an Asian insect, contains a high percentage of trihy-

[ Obtained by setting up the ratio

droxypalmitic acid - CH3(CH2)11(CHOH)3COOH [2]. This mole-180

cule contains a low percentage of oxygen and produces a high 192

1.00

heat /gram value. Red gum is a complex mixture obtained from an Australian tree, with excellent fuel characteristics and a low and solving

melting point to aid in ignition.

Charcoal is another organic fuel, and has been employed in X = (180)(1.00) = 0.938]

1 92

high-energy mixtures for over a thousand years. It is prepared by heating wood in an air-free environment ; volatile products FIG. 3.1 Calculation of oxygen demand. The quantity of oxygen are driven off and a residue that is primarily carbon remains.

consumed during the combustion of an organic fuel can be calcu-Shimizu reports that a highly-carbonized sample of charcoal lated by first balancing the equation for the overall reaction. Each showed a 91:3:6 ratio of C, 11, and 0 atoms [2].

carbon atom in the fuel converts to a carbon dioxide molecule (C0

The pyrotechnic behavior of charcoal may vary greatly de-2 ),

and every two hydrogen atoms yield a water molecule. The oxy-pending upon the type of wood used to prepare the material.

gen required to burn the fuel is determined by adding up all of The surface area and extent of conversion to carbon may vary the atoms of oxygen in the products and then subtracting the oxy-widely from wood to wood and batch to batch, and each prepara-gen atoms (if any) present in the fuel molecule. The difference is tion must be checked for proper performance [13]. Historically, the number of oxygen atoms that must be supplied by the atmos-willow and alder have been the woods preferred for the prepara-phere (or by an oxidizer). This number is then divided by 2 to tion of charcoal by black powder manufacturers.

obtain the number of

Charcoal is frequently the fuel of choice when high heat and 02 molecules needed. The coefficients can

then be multiplied by the appropriate molecular weights to obtain gas output as well as a rapid burning rate are desired. The ad-the number of grams involved.

dition of a small percentage of charcoal to a sluggish composition will usually accelerate the burning rate and facilitate ignition.

Larger particles of charcoal in a pyrotechnic mixture will produce attractive orange sparks in the flame, a property that is I

often used to advantage by the fireworks industry.

26.9% glucose by weight. An identical answer is obtained if the chemical equation for the reaction between KC1O 3 and glucose is Carbohydrates

balanced and the molar ratio then converted to a weight ratio The carbohydrate family consists of a large number of naturally-occurring oxygen-rich organic compounds. The simplest carbo-C 6H 120 6 + 4 KC1O 3 -> 6 CO2 + 6 H 2O + 4 KC1

hydrates - or "sugars" - have molecular formulas fitting the Moles :

pattern (C.H 2O)n , and appeared to early chemists to be "hy-Grams:

180

490

drated carbon." The more complex members of the family de-Weight %:

26.9

73.1

viate from this pattern slightly.

Examples of common sugars include glucose (C 6H120 6 ) , lactose The more highly oxidized - or oxygen rich - a fuel is, the (C12H22011) , and sucrose (C12H22011) . Starch is a complex poly-smaller its heat output will be when combusted. The flame tem-mer composed of glucose units linked together. The molecular perature will also be lower for compositions using the highly-ox-formula of starch is similar to (C6H1005)n, and the molecular idized fuel. Also, fuels that exist as hydrates (containing water weight of starch is typically greater than one million. Reaction e

Chemistry

Components

o f Pyrotechnics

of High-Energy Mixtures

with acid breaks starch down into smaller units. Dextrine, a found in a handbook prepared by the U.S. Army [3]. Table 3.6

widely-used pyrotechnic fuel and binder, is partially-hydrolyzed contains information on a variety of organic compounds that are starch. Its molecular weight, solubility, and chemical behavior of interest to the high-energy chemist.

may vary considerably from supplier to supplier and from batch to batch. The testing of all new shipments of dextrine is required in pyrotechnic production.

BINDERS

The simpler sugars are used as fuels in various pyrotechnic mixtures. They tend to burn with a colorless flame and give off A pyrotechnic composition will usually contain a small percentage less heat per gram than less-oxidized organic fuels. Lactose is of an organic polymer that functions as a binder, holding all of used with potassium chlorate in some colored smoke mixtures to the components together in a homogeneous blend. These bind-produce a low-temperature reaction capable of volatilizing an orers, being organic compounds, will also serve as fuels in the ganic dye with minimum decomposition of the complex dye mole-mixture.

cule. The simpler sugars can be obtained in high purity at mod-Without the binder, materials might well segregate during erate cost, making them attractive fuel choices. Toxicity prob-manufacture and storage due to variations in density and par-lems tend to be minimal with these fuels, also.

ticle size. The granulation process, in which the oxidizer, fuel, and other components are blended with the binder (and usually a suitable solvent) to produce grains of homogeneous composi-Other Organic Fuels

tion, is a critical step in the manufacturing process. The sol-The number of possible organic fuels is enormous. Considera-vent is evaporated following granulation, leaving a dry, homoge-tions in selecting a candidate are:

neous material.

Dextrine is widely used as a binder in the fireworks industry.

Water is used as the wetting agent for dextrine, avoiding the 1. Extent of oxidation: This will be a primary factor in the cost associated with the use of organic solvents.

heat output /gram of the fuel.

Other common binders include nitrocellulose (acetone as the 2. Melting point: A low melting point can aid in ignitibility solvent), polyvinyl alcohol (used with water), and Laminae (an and reactivity; too low a melting point can cause produc-unsaturated polyester crosslinked with styrene -- the material tion and storage problems. 100°C might be a good mini-is a liquid until cured by catalyst, heat, or both, and no sol-mum value.

vent is required). Epoxy binders can also be used in liquid 3. Boiling point: If the fuel is quite volatile, the storage form during the mixing process and then allowed to cure to life of the mixture will be brief unless precautions are leave a final, rigid product.

taken in packaging to prevent loss of the material.

In selecting a binder, the chemist seeks a material that will 4. Chemical stability: An ideal fuel should be available com-provide good homogeneity with the use of a minimum of polymer.

mercially in a high state of purity, and should maintain Organic materials will reduce the flame temperatures of compo-that high purity during storage. Materials that are easily sitions containing metallic fuels, and they can impart an orange air-oxidized, such as aldehydes, are poor fuel choices.

color to flames if incomplete combustion of the binder occurs and 5. Solubility: Organic fuels frequently double as binders, carbon forms in the flame. A binder should be neutral and non-and some solubility in water, acetone, or alcohol is re-hygroscopic to avoid the problems that water and an acidic or quired to obtain good binding behavior.

basic environment can introduce. For example, magnesium-containing mixtures require the use of a non-aqueous binder/sol-Materials that have been used in pyrotechnic mixtures include vent system, because of the reactivity of magnesium metal to-nitrocellulose, polyvinyl alcohol, stearic acid, hexamethylenetetra -

wards water. When iron is used in a composition, pretreatment mine, kerosene, epoxy resins, and unsaturated polyester resins of the metal with wax or other protective coating is advisable, such as Laminae. The properties of most of these fuels can be especially if an aqueous binding process is used.

Chemistry of Pyrotechnics

Components of High-Energy Mixtures

RETARDANTS

U.S. Army Material Command, Engineering Design Handbook, Military Pyrotechnic Series, Part Three, "Proper-Occasionally, a pyrotechnic mixture will function quite well and ties of Materials Used in Pyrotechnic Compositions,"

produce the desired effect, except for the fact that the burning Washington, D.C., 1963 (AMC Pamphlet 706-187).

rate is a bit too fast. A material is needed that will slow down 4.

R. C. Weast (Ed.), CRC Handbook o f Chemistry and the reaction without otherwise affecting performance. This can Physics, 63rd Ed., CRC Press, Inc., Boca Raton, Fla., be accomplished by altering the ratio of ingredients (e.g., re-1982.

ducing the amount of fuel) or by adding an inert component to 5.

H. Ellern, Military and Civilian Pyrotechnics, Chemical the composition. Excess metallic fuel is less effective as a "cool-Publ. Co., Inc., New York, 1968.

ant" because of the ability of many fuels - such as magnesium -

T. J. Barton, et al. , "Factors Affecting the Ignition Tem-to react with the oxygen in air and liberate heat. Also, metals perature of Pyrotechnics," Proceedings, Eighth Interna-tend to be excellent heat conductors, and an increase in the tional Pyrotechnics Seminar, IIT Research Institute, metal percentage can speed up a reaction by facilitating heat Steamboat Springs, Colorado, July, 1982, p. 99.

transfer through the composition during the burning process.

J. H. McLain, Pyrotechnics from the Viewpoint of Solid Materials that decompose at elevated temperatures with the State Chemistry, The Franklin Institute Press, Philadelphia, absorption of heat (endothermic decomposition) can work well Penna., 1980.

as rate retardants.

Calcium and magnesium carbonate, and so-

U.S. Department of Transportation, "Hazardous Materials dium bicarbonate, are sometimes added to a mixture for this pur-Regulations," Code of Federal Regulations, Title 49, Part pose.

173.

heat

U.S. Army Material Command, Engineering Design Hand-CaCO 3 (solid)

CaO (solid) + CO 2 (gas)

book, Military Pyrotechnic Series, Part One, "Theory and 2 NaHCO

Application," Washington, D.C., 1967 (AMC Pamphlet 706-3

(solid) --> Na 20 (solid) + H 2O (gas) + 2 CO 2 (gas) 185).

However, gas generation occurs that may or may not affect the 10.

D. Price, A. R. Clairmont, and I. Jaffee, "The Explosive performance of the mixture.

Behavior of Ammonium Perchlorate," Combustion and Flame, Although endothermic, these reactions are thermodynamically 11, 415 (1967).

spontaneous at high temperature due to the favorable entropy 11.

R. Lancaster, Fireworks Principles and Practice, Chemical change associated with the formation of random gaseous prod-Publ. Co., Inc., New York, 1972.

ucts from solid starting materials.

12.

U.S. Consumer Product Safety Commission, "Fireworks De-Inert diluents such as clay and diatomaceous earth can also vices," Code of Federal Regulations, Title 16, Part 1507.

be used to retard burning rates. These materials absorb heat J. E. Rose, "The Role of Charcoal in the Combustion of I

13.

and separate the reactive components, thereby slowing the py-Black Powder," Proceedings, Seventh International Pyro-rotechnic reaction.

technics Seminar, IIT Research Institute, Vail, Colorado, July, 1980, p. 543.

REFERENCES

A. A. Shidlovskiy, Principles of Pyrotechnics, 3rd Ed., Moscow, 1964. (Translated by Foreign Technology Division, Wright-Patterson Air Force Base, Ohio, 1974.) 2.

T. Shimizu, Fireworks - The Art, Science & Technique,

pub. by T. Shimizu, distrib. by Maruzen Co. , Ltd., Tokyo, 1981.

A pyrotechnician cautiously mixes a composition through a sieve to achieve homogeneity. Eye and respiratory protection are worn, and great care is taken throughout this critical phase of the manufacturing process. Sensitive compositions, as well as large quantities of any pyrotechnic mixture, should be blended remotely. (Fireworks by Grucci)

4PYROTECHNIC PRINCIPLES

INTRODUCTION

The "secret" to maximizing the rate of reaction for a given pyrotechnic or explosive composition can be revealed in a single word -

homogeneity. Any operation that increases the degree of intimacy of a high-energy mixture should lead to an enhancement of reactivity. Reactivity, in general, refers to the rate - in grams or moles per second - at which starting materials are converted into products.

The importance of intimate mixing was recognized as early as 1831 by Samuel Guthrie, Jr. , a manufacturer of "fulminating powder" used to prime firearms. Guthrie's mixture was a blend of potassium nitrate, potassium carbonate, and sulfur, and he discovered that the performance could be dramatically improved if he first melted together the nitrate and carbonate salts, and then blended in the sulfur. He wrote, "By the previously melting together of the nitro and carbonate of potash, a more intimate union of these substances was effected than could possibly be made by mechanical means" [1]. However, he also experienced the hazards associated with maximizing reactivity, reporting, "I doubt whether, in the whole circle of experimental philosophy, many cases can be found involving dangers more appalling, or more difficult to be overcome, than melting fulminating powder and saving the product, and reducing the process to a business operation. I have had with it some eight or ten tremendous explosions, and in one of them I received, full in my face and eyes, the flame of a quarter of a pound of the 83

Chemistry of Pyrotechnics

Pyrotechnic Principles

composition, just as it had become thoroughly melted" [1]. An TABLE 4.1 Representative Heats of Reaction for enormous debt is owed to these pioneers in high-energy chemis-Pyrotechnic Systemsa

try who were willing to experiment in spite of the obvious hazards, and reported their results so others could build on their o Hreaction ,

knowledge.

Composition (% by weight)

kcal /gram

Application

Varying degrees of homogeneity can be achieved by altering either the extent of mixing or the particle size of the various Magnesium

2.0

Illuminating flare

components. Striking differences in reactivity can result from changes in either of these, as Mr. Guthrie observed with his Sodium nitrate, NaNO 3

"fulminating powder."

Laminac binder

A number of parameters related to burning behavior can be experimentally measured and used to report the "reactivity" or Potassium perchlorate, KCIO

performance of a particular high-energy mixture [2]: 4 60

1.8

Photoflash

Aluminum

1. Heat of reaction : This value is expressed in units of Boron

1.6

I gniter

calories (or kilocalories) per mole or calories per gram, and is determined using an instrument called a "calorime-Potassium nitrate, KNO 3

ter." One calorie of heat is required to raise the tempera-VAAR binder

ture of one gram of water by one degree (Celsius) , so the temperature rise of a measured quantity of water, brought Potassium nitrate, KNO

about by the release of heat from a measured amount of 3

1.0

Starter mixture

high-energy composition, can be converted into calories Charcoal

of heat. Depending upon the intended application, a mixture liberating a high, medium, or low value may be de-Black powder

0.85

Flash and report

sired. Some representative heats of reaction are given in Aluminum

Military simulator

Table 4. 1.

2. Burning rate: This is measured in units of inches, cen-Barium chromate, BaCr0

0.5

Delay mixture

timeters or grams per second for slow mixtures, such as 4

delay compositions, and in meters per second for "fast"

Boron

materials. Burning rates can be varied by altering the materials used, as well as the ratios of ingredients, as Silicon

0.28

First fire mixture

shown in Table 4.2. Note: Burning "rates" are also Red lead oxide, Pb

sometimes reported in units of seconds /cm or seconds/

30,,

gram - the inverse of the previously-stated units. Al-Titanium

ways carefully read the units when examining burning rate data!

Tungsten

0.23

Delay mixture

3. Light intensity: This is measured in candela or candle-Barium chromate, BaCrO,,

power. The intensity is determined to a large extent by the temperature reached by the burning composition. In-Potassium perchlorate, KC10 y 10

tensity will increase exponentially as the flame temperature rises, provided that no decomposition of the emitting spe-aSource: F. L. McIntyre, "A Compilation of Hazard and Test Data cies occurs.

for Pyrotechnic Compositions," Report AD-E400-496, U.S. Army 4. Color quality: This will be determined by the relative in-Armament Research and Development Command, Dover, New Jersey, tensities of the various wavelengths of light emitted by October 1980.

pyrotechnic Principles

Chemistry of Pyrotechnics

TABLE 4.2 Burning Rates of Binary Mixtures of Nitrate Oxidizers with Magnesium Metala

Burning rate (inches/minute)b

Barium nitrate

Potassium nitrate

% Oxidizer

oxidizer,

(by weight)

% Magnesium

Ba(NO 3) 2

KNO 3

2.9

2.3

4.7

5.1

10.7

8.5

16.8

13.3

38.1

21.8

40.3

29.3

"Erratic"

26.4

aReference 2.

FIG. 4.1 Light output from a green flare. The radiant output bLoading pressure was 10,000 psi into 1.4 in' cases.

from a burning pyrotechnic composition can be analyzed using an instrument known as a spectrophotometer. Energy output can be monitored as a function of wavelength. A good "white light" mixture will emit reasonably intense light over the entire visible region. Color will be produced when the emission species present in the pyrotechnic flame. Only those wave-is concentrated in a narrow portion of the visible range. The lengths falling in the "visible" region of the electromag-output from this flare falls largely between 500-540 nm -- the netic spectrum will contribute to the color. An emission

"green" portion of the visible spectrum. Green light emission spectrum, showing the intensity of light emitted at each is usually associated with the presence of a barium compound wavelength, can be obtained if the proper instrumenta -

in the mixture, with molecular BaCI in the vapor state, typi-tion - an emission spectrometer - is available (Figure 4.1).

cally the primary emitter of green light. The mixture pro-5. Volume o f gas produced: Gaseous products are frequently ducing this emission pattern consisted of potassium perchlor-desirable when a high-energy mixture is ignited. Gas can ate (32.5%), barium nitrate (22.5%), magnesium (21%), copper be used to eject sparks, disperse smoke particles, and pro-powder (7%), polyvinyl chloride (12%), and 5% binder. Source vide propellant behavior; when confined, gas can be used H. A. Webster III, "Visible Spectra of Standard Navy Colored to create an explosion. Water, carbon monoxide and di-Flares," Proceedings, Pyrotechnics and Explosives Applications oxide, and nitrogen are the main gases evolved from high-Section, American Defense Preparedness Association, Fort energy mixtures. The presence of organic compounds can Worth, Texas, September, 1983.

Chemistry of Pyrotechnics

Pyrotechnic Principles

generally be counted upon to produce significant amounts TABLE 4. 3 Effect of Particle Size on Performance of a of gas. Organic binders and sulfur should be avoided if Flare Compositiona

a "gasless" composition is desired.

6. Efficiency: For a particular composition to be of practi-Average particle

cal interest, it must produce a significant amount of pyro-Composition :

Component

% by weight

size

technic effect per gram of mixture. Efficiency per unit volume is also an important consideration when available Magnesium metal

see table below

space is limited.

Sodium nitrate,

34 micrometers

7. Ignitibility : A pyrotechnic composition must be capable NaNO

of undergoing reliable ignition, and yet be stable in 3

(10 -6 meters)

transportation and storage. The ignition behavior of Laminae binder

every mixture must be studied, and the proper ignition Polyvinyl chloride

27 micrometers

system can then be specified for each. For easily-ignited materials, the "spit" from a burning black powder fuse is Magnesium average

Flare burning

often sufficient. Another common igniter is a "squib" or particle size,

Flare candlepower

rate, inches/

electric match, consisting of a metal wire coated with a micrometers

(1,000 candles)

minute

small dab of heat-sensitive composition. An electric current is passed through the wire, producing sufficient heat 437

130

2.62

to ignite the squib. The burst of flame then ignites the main charge. For pyrotechnic mixtures with high ignition 322

154

3.01

temperatures, a primer or first fire is often used. This 168

293

5.66

is an easily-ignited composition that can be activated by a fuse or squib. The flame and hot residue produced are 110

285

5.84

used to ignite the principal material. This topic will be treated in more detail in Chapter 5.

aReference 2.

To produce the desired pyrotechnic effect from a given mixture, the chemist must be aware of the large number of variables that can affect performance. These factors must be held constant from batch to batch and day to day to achieve reproducible behavior.

size, the more reactive a particular composition should be, Substantial deviations can result from variations in any of the with all other factors held constant. Table 4. 3 illustrates following [2]:

this principle for a sodium nitrate /magnesium flare composition. Note the similarity in performance for the two 1. Moisture: The best rule is to avoid the use of water in smallest particle sizes, suggesting that an upper per-processing pyrotechnic compositions, and to avoid the use formance limit may exist.

of all hygroscopic (water-attracting) ingredients. If wa-3. Surface area of the reactants: For a high-energy reaction ter is used to aid in binding and granulating, an efficient to rapidly proceed, the oxidizer must be in intimate contact drying procedure must be included in the manufacturing with the fuel. Decreasing particle size will increase this process. The final product should be analyzed for mois-contact, as will increasing the available surface area of the ture content, if reproducible burning behavior is critical.