The following article was originally published as RDTN No.

71, 20 March 1964

by the U. S. Naval Ammunition Depot, Crane, Indiana, USA

Theory of Colored Flame Production

B. E. Douda, Research Chemical Engineer

Research and Development Department

ABSTRACT
The theories and attributes associated with the production of colored flames are presented. Par-
ticular attention is given to flames containing strontium (red), barium (green), sodium (yellow) and
copper (green or blue). Thermal excitation of vaporized neutral atoms, molecules and ions is corre-
lated with the emission of atomic, band and ionic spectra. These spectra are tabulated. The color con-
tribution of C-type chemiluminescence, a non-thermal excitation, is described briefly.
The variability of emitters, emissions and color with the operating flame temperature is discussed
in relation to the thermodynamic properties of the reactants and the products of combustion. These
thermal properties are tabulated. Ionization is shown as a contributor to color degeneration. The use
of an ionization buffer to reduce ionization is explained.
Depending on flame conditions and the metal being used, the influence of halogens on the produc-
tion of color is discussed. The influence is not always beneficial. The flame equilibrium shift caused by
the halogens is described for each of the metals. Metals and anions other than the halides are dis-
cussed in relation to their ability to intensify or suppress emission. The preferred emitters for each of
the metals are listed, and idealistic postulates are presented which apply to the production of color in
a flame.

Note added in proof by author:

At the time that these notes were written, some 35 years ago, I was quite naïve with respect to the
combustion phenomenology and, as a consequence, I wrote an oversimplified explanation for what are
very complicated events. In addition, I had not been introduced to such branches of learning as quan-
tum mechanics, spectroscopy, combustion science, and related fields until much later in my career.
That void of knowledge tends to explain why the presentation of these notes is approached qualita-
tively and in an unrefined manner. Finally, as a young scientist without a mentor, in retrospect, it
seems quite presumptuous to have entitled these notes the “Theory of Colored Flame Production”,
when in fact, not much “theory” is included. Nevertheless, most of the recorded information is of
value, even to this day. The reader’s considerateness is appreciated.

The information contained in this document represents the opinions of the author and hence should not
be construed to represent the official policy of any other individual or organization.

Theory of Colored Flame Production — Douda Page 1

 Theory of Colored Flame Production

1. Purpose
a. The purpose of this presentation is to enumerate and discuss the theories and attributes associ-
ated with the production of colored flames.

2. Introduction
a. Ellern[16] states, “… colored flame production is beset with unusual problems. These problems
are caused by the lack of choice in the available color-creating materials, the absorption of
light by the atmosphere, the limits of discrimination by the human eye, and the chemistry and
physics of the processes and substances involved.” To overcome the “lack of choice” problem,
additional color-creating materials can be made available by inorganic, organic and metal-
organic chemical synthesis. In order to evaluate new materials, it is necessary to establish cri-
teria by which the material may be judged.
b. If the chemistry and physics of the processes involved in colored flame production were
known in detail, it would not be difficult to establish the criteria. Because, however, much in-
formation is not available, it is often necessary to judge materials by empirical methods.
Ellern[15] summarized most of the problem when he stated, “With increased and fuller knowl-
edge of the heats of formation, boiling points and dissociation temperatures of reaction prod-
ucts; and with greater insight into the emitting characteristics of gaseous flames and of solid
particles, we should eventually be able to build formulas in a more rational manner. Even so,
compromises are unavoidable. Maximum heat output per unit volume, highest stability, and
lowest volatility of end products (lowest volatility for white light, highest volatility for colored
light), and desirable behavior of original reactants, may not be attainable in one formula”. One
should not interpret this to mean that there is a complete void of knowledge of the chemical
and physical processes related to colored light production. Certain facts and theories are avail-
able which can be used first to describe the process by which a colored flame is produced and
secondly to evaluate and judge the value of new compounds intended for use in colored light
formulations. It is for this purpose that the theories related to colored flame production were
collected, formulated and discussed in this presentation.

3. Colored Flame Production

a. Mechanism
1. Only a few of the more than 100 elements are used to impart a color to a pyrotechnic
flame. These are strontium (red), barium (green) copper (green or blue) and sodium (yel-
low). Ellern[13] states that lithium (red), boron (green), thallium (green), rubidium (red) and
cesium (blue) are also strong color producers but that their use is not practical because of
cost, toxicity or the nature of the compounds. All of these elements have certain properties
and characteristics in common which contribute to colored light emission.
2. Colored flames are produced by excitation of metallic spectra. At the high temperature of
the flame, the salt or metal is vaporized, and part or all of the gaseous molecules are pro-
gressively dissociated to give neutral atoms that are potentially emitting species. Some of
the free metal atoms unite with other radicals or atoms present in the flame. The vapors of
the neutral metal atoms, or of the molecules containing the metal atom, are then excited by

Page 2 Theory of Colored Flame Production — Douda

 Figure 1.

the thermal energy of the flame. Ionization and excitation of the neutral atoms may occur
to some degree. From the excited levels of the atom, or molecule, or ion, a reversion takes
place to the ground state - partly by impacts with other species, partly spontaneously by
emission of light. The preceding sequence[2] of events occurs in rapid succession. Figure 1
may help to visualize the entire sequence if strontium chloride is used as the example.
b. Spectrum vs. Emitter
1. Different wavelengths of radiation are emitted whenever different events occur. No useful
radiation (with respect to colored flames) results while the metal or metallic compound is
a solid or liquid. As soon as it is vaporized, useful radiation may result. If the compound
remains as an undissociated vaporized molecule, it produces a band spectrum. When the
temperature is reached that causes the compound to dissociate to vaporized neutral atoms,
a different spectrum results. Neutral atoms produce an atomic spectrum composed of
atomic (arc) lines. When the temperature is increased further to the point that the electron
is completely removed from the influence of the nucleus, the atom is ionized. Ionized at-
oms produce an ionic spectrum composed of ionic (spark) lines.
2. Now that a specific event has been described as being associated with a specific spectrum,
the sequence of events shown in Figure 1 will be reviewed. The solid Sr° metal or SrCl2
molecule is vaporized. The SrCl2 molecule dissociates to SrCl. The gaseous undissociated
SrCl molecules emit a band spectrum. The gaseous neutral atoms of Srº emit an atomic
spectrum. The gaseous neutral Srº atoms are obtained from the vaporization of the neutral
Srº metal or the dissociation of the gaseous SrCl molecule. At this point, one of two things
can happen to the neutral Srº atom. It can be heated until it ionizes, at which time it emits
an ionic spectrum, or it can combine with an anion such as the hydroxide, OH, radical to
form molecular SrOH. This new molecule will emit a band spectrum and will behave like
the SrCl molecules. As long as it remains as an undissociated gaseous molecule, it will
emit a band spectrum. When the temperature is raised, such that the SrOH dissociates into
the neutral Srº atom and the OH radical, the Sr° will once again emit an atomic spectrum.
It should be obvious by now that the entire system is temperature dependent.
3. Up to this point, spectra were discussed in terms of radiation resulting from thermal exci-
tation. When radiation results from non-thermal excitation it is described as one of three
types of chemiluminescence. For purposes of colored pyrotechnic flames, the C-type

Theory of Colored Flame Production — Douda Page 3

 chemiluminescence[31,36] is most important. It results from the formation of an excited
molecule directly in the excited state in amounts bearing little or no relation to the ground-
state concentrations. This is a molecular, as opposed to an atomic, phenomenon. Colorful
band systems for metallic-OH molecules, particularly for barium, strontium and copper,
are probably due to molecules that have no independent[5] existence outside the flame. An
equation representative of the C-type chemiluminescence is
Cu + OH + X → CuOH + X
where X is a third body such as H2O, H2 or N2 and CuOH is the directly formed excited
molecule. Gaydon[20,22] discusses chemiluminescence in relation to flame reaction proc-
esses and equilibria.
4. There is a group of molecular emitters that do not provide desirable colors to pyrotechnic
flames. Some of these emitters are OH, CO, O2, CH, C2 and H2O. They make up the back-
ground radiation of the flame and will be present as long as organic binders or metal-
organic compounds are used in colored flares. All of these radicals and molecules emit a
band spectrum.
5. Another spectrum that exists in colored-flame pyrotechnics is due to continuous radiation
and is called a continuous spectrum or continuum. No metal is free from a continuous
spectrum, especially when present in large amounts. The continuous spectrum is normally
a very wide, undifferentiated band.
6. For details concerning the theory of spectra, the reader is referred to books by Gaydon[18]
and Pauling.[29]
7. Not only do different metals emit different spectra, but also any given metal may radiate
several spectra simultaneously. To complicate the matter even more, all the lines and
bands responsible for the colors in colored flare flames have not been assembled in com-
posite form. Therefore, to fill this void and to make information readily available for ref-
erence in later discussion, data were assembled concerning the important lines, bands and
continuum for strontium, barium, copper, sodium, lithium, boron, thallium, rubidium, ce-
sium and potassium. These data are in Appendix I.
c. Emitters vs. Temperature and Color
1. Thus far, it has been established that gaseous metals or metallic compounds will emit
various spectra when excited in a flame. The different types of spectra were introduced in
relation to the degree or type of excitation involved. The elements that impart a strong red,
green, yellow or blue color to a flame were listed. It was also stressed that the flame spec-
trum that results from the metal excitation is temperature dependent. If the composition of
the flame is known to the extent that the emitters are identified, the flame spectrum corre-
sponding to these emitters will be composed predominantly of energy radiating in wave-
lengths which the eye associates with a particular color. Thus, the apparent color of a py-
rotechnic flame can be explained by relating the wavelengths of energy that correspond to
that color with emitters that radiate in that wavelength. As mentioned previously, the exis-
tence in, or absence from, a flame of a given emitter species is related to the flame tem-
perature. Therefore, in an effort to describe the color production mechanism, it is not only
necessary to identify the emitting species but also it is necessary to specify the flame tem-
perature.

Page 4 Theory of Colored Flame Production — Douda

 d. Temperature
1. For purposes of this discussion, colored pyrotechnic flames will be described assuming a
flame temperature of 2000 K. Most colored pyrotechnic flames will probably exceed that
temperature. In comparison to other flames, the 2000 K reference temperature is equal to
the temperature of an illuminating gas-air flame. The maximum theoretical temperature of
an oxygen-hydrogen flame[1] is about 3050 K and that of an oxygen-acetylene flame is
about 3325 K. Dean[6] gives 2450 K as the operating temperature of an oxygen-hydrogen
flame and 2800 K for an oxygen-acetylene flame. The seemingly low reference tempera-
ture was selected primarily to later show that many molecular substances are decomposed
below this temperature and, therefore, cannot be considered as emitters at or above this
temperature. The reader is referred to Gaydon[23] for information concerning the measure-
ment of flame temperature.
2. There are several temperature-energy relationships that will be used for estimating certain
occurrences. For example, in an oxygen-acetylene flame (2800 K), emission is limited to
lines[3] whose excitation potential is less than ~5.5 εν or 127 kcal/mole. One electron volt
per molecule[21] is equivalent to 23.053 kilocalories per gram mole. At 2000 K, it is esti-
mated that molecules with a dissociation energy of 75 kcal/mole (3.26 εν/molecule) or less
will not be present in an appreciable amount and that molecules with a dissociation energy
of 95 kcal/mole (4.13 εν/molecule) and larger can be formed and will be stable.
Nominally, the 2000 K flame is equated to 3.7 εν/molecule or 30 kcal/mole. For diatomic
molecules, the dissociation energy[30] is related to the heat of formation and to bond
strength.
3. It is emphasized that the preceding relationships were presented for estimating purposes
and must not be used quantitatively. The reason for this obvious lack of accuracy results
from the lack of complete understanding of pyrotechnic flame mechanisms. The high tem-
perature chemistry involved is not always predictable using room temperature theory.
Brewer and Searcy[12] were quoted as having defined high temperature chemistry as the
chemistry of systems at sufficiently high temperatures so that the oxidation states, com-
pounds and general chemical behavior differ appreciably from those at room temperature.
This definition emphasizes the probability that new and possibly unorthodox theories must
be formulated to explain high temperature phenomena.
e. Energy Definitions and Relationships
1. Various energy terms have already been used in this presentation. To make certain their
usage is understood, they are defined[39] as:
a) Excitation Potential = Excitation Energy:
1) The energy necessary to bring an atom, molecule, atomic nucleus, etc., from the
ground state into an excited state. Example of use: In Appendix I the atomic spec-
trum strontium line λ4607.3 is shown with an excitation potential of 2.7 electron
volts. Thus, 2.7 εν/molecule is necessary to excite this strontium line. From the
preceding discussion of temperature, a 2000 K flame was approximated as 3.7
εν/molecule or 85 kcal/mole. A 2000 K flame, therefore, has sufficient energy to
excite the λ4607.3 atomic spectrum strontium line but will not excite the 4.3 εν
atomic spectrum strontium line λ4832.l. With knowledge of the flame temperature
and its relationship to energy, the excitation potential is a measure used to deter-
mine whether or not a particular spectrum line will be emitted.
b) Ionization Potential = Ionization Energy:

Theory of Colored Flame Production — Douda Page 5

 1) The energy per unit charge, for a particular kind of atom, necessary to remove an
electron from the atom to infinite distance. Example of use: In Appendix I the
ionic spectrum strontium line λ4077.7 is shown with an excitation potential of 8.7
εν. The ionization potential for strontium is shown as 5.69 εν. Thus, 5.69 εν is
necessary to remove the first electron from the influence of the strontium nucleus
and an additional 3.01 εν is necessary to excite the λ4077.7 ionic line for stron-
tium. The previous discussion of temperature compared the oxygen-acetylene
flame to 5.5 εν. Thus, the oxygen-acetylene flame cannot be expected to excite the
λ4077.7 ionic line to any appreciable degree. Some ionization of strontium will,
however, occur. The first ionization potentials[27] for the 10 elements being
discussed are:

Element kcal/mole Electron volts

Lithium 124.3 5.39
Sodium 118.4 5.14
Potassium 100.0 4.34
Rubidium 96.3 4.18
Cesium 89.7 3.89
Thallium 140.8 6.11
Barium 120.1 5.21
Strontium 131.2 5.69
Boron 191.2 8.29
Copper 178.1 7.73

c) Dissociation Energy:
1) The energy necessary for the complete separation from each other of the two at-
oms forming a diatomic molecule, or for the removal of an atom or a group of at-
oms from a polyatomic molecule. More exactly, the dissociation energy is the dif-
ference between the energy of the molecule and its dissociation products in their
respective ground states. If, therefore, the actual dissociation process leads to at-
oms (or radicals) in excited states the dissociation energy is the energy needed for
their separation minus the excitation energy. Example of use: Dissociation ener-
gies for various diatomic and polyatomic molecules are listed in Appendix II.
These values in conjunction with the heat of formation and free energy of forma-
tion are used to hypothesize the existence of molecules in a flame. Sodium hy-
dride, for example, has a low dissociation energy and heat of formation and
slightly negative free energy of formation. Conversely, these thermodynamic
characteristics are numerically large for sodium fluoride. Thus, at high tempera-
tures, sodium fluoride would be expected to be stable whereas sodium hydride
would be expected to decompose.
d) Enthalpy = Heat Content, H.
1) Thermodynamic potential defined as
H = E + PV
where E is the internal energy of the system and PV is pressure-volume.
e) Heat of Formation
1) The increase of heat content of the system when one mole of a substance is
formed from its elements. Example of use: Heats of Formation for various com-
pounds are listed in Appendix II. In a manner similar to that described for disso-

Page 6 Theory of Colored Flame Production — Douda

 ciation energy, heat of formation is used as a measure to estimate the existence of
a compound in a flame at high temperature. This means is somewhat unreliable
because of entropy changes.
f) Entropy, S.
1) The energy[33] per degree of absolute temperature that cannot be recovered as
work. Entropy, S, is related to free energy and enthalpy by
H = F + TS
g) Free Energy of Formation, ΔF
1) The free energy[35] change accompanying the formation of the compound at unit
activity from the elements also at unit activity. Free energy of formation is defined
by the relationship
ΔF = ΔH – TΔS
Example of use: The sign of the free energy[34] change of a process is very sig-
nificant. A minus sign denotes that the reaction tends to proceed spontaneously. A
positive sign indicates that the reaction is nonspontaneous and when ΔF = 0, the
system is at equilibrium. A negative free energy change for a process does not
necessarily mean that the process will take place. It is merely an indication that the
process can occur, provided the conditions are right. It is the sign of the free
energy change that determines whether the potentiality to react exists, and it is the
magnitude of the free energy change that tells how large that potentiality is. Thus,
the free energy of formation of a compound may be used to hypothesize the exis-
tence of the compound in a flame. Free energies of formation at 2000 K are given
for many compounds in Appendix II.
f. Ionization
1. Ten elements have been mentioned previously as being associated with the production of a
colored flame. It is interesting to note that five of these are in Group I of the Periodic
Table. They are lithium, sodium, potassium, rubidium and cesium. Two of the ten ele-
ments, barium and strontium, are in Group II of the Periodic Table. In addition, these
seven also have ionization potentials of such magnitude that ionization in a flame can be
expected. Table 1 gives the percent ionization[6] of the aforementioned seven elements in
relation to various operating flame temperatures.

Table 1. Percent Ionization Relative to Various Operating Flame Temperatures.

Ionization Air- Hydrogen- Acetylene-

Potential Propane Oxygen Oxygen
Element εν 2200 K 2450 K 2800 K
Lithium 5.39 <0.01 0.9 16.1
Sodium 5.14 0.3 5.0 26.4
Potassium 4.34 2.5 31.9 82.1
Rubidium 4.18 13.5 44.4 89.6
Cesium 3.89 28.3 69.6 96.4
Strontium 5.69 <0.1 2.7 17.2
Barium 5.21 1.0 8.6 42.8

The Saha equation,

Theory of Colored Flame Production — Douda Page 7

 −5050 E 5 [ g + ][ g − ]
log K = + log T − 6.50 + log
T 2 [g]
where E is the ionization potential in electron volts, T the absolute temperature and the g
terms are the statistical weight of the ionized atom, the electron and the neutral atom, is
used to determine the change in the degree of ionization with temperature. For alkali
(Group I) metals the final term is zero; for the alkaline earth (Group II) metals the final
term is 0.6.
2. At 2200 K, except for rubidium and cesium, Table 1 shows very little ionization. Thus, at
the 2000 K reference temperature chosen for this presentation, even less ionization can be
expected. An increase of relatively few degrees to 2450 K shows a significant increase in
ionization. Therefore, unless the flare is operating near or below 2200 K, a significant
amount of ionization must be anticipated.
3. For purposes of colored flame production, there are several flame characteristics associ-
ated with ionization that make ionization undesirable. This is, of course, why pyrotechnic
formulators have always attempted to create "cool" burning compositions. The spectrum[4]
of the ion is completely different from the spectrum of the neutral atom and resembles the
spectrum emitted by the element of preceding atomic number. However, because of the
additional positive charge on the nucleus, the zero energy level is higher than for the ele-
ment of preceding atomic number, and consequently the emission lines are displaced to-
ward the ultraviolet. Therefore, when appreciable ionization occurs a reduced quantity of
the desired wavelength of energy is emitted and as a result, the flame color deteriorates.
This occurs first because the ion is emitting an ionic spectrum which, for pyrotechnic pur-
poses, is undesirable and secondly because of that ionization, a reduced number of neutral
atoms are left to emit in the desired atomic spectrum or to form molecules that would emit
the desired band spectrum.
4. If ionization occurs in a flame dependent on barium for its color, the deterioration in color
becomes more noticeable than it would in a comparable sodium or strontium dependent
flare because:
a) Many emissions within the desirable atomic and band spectra are in the yellowish-
green wavelength instead of deep green to blue-green and therefore do not, even under
ideal conditions, provide a large contrast with yellow...and
b) The intensity of the barium spectrum is less than that of strontium or sodium and
therefore any reduction in emission due to ionization will be more noticeable...and
c) Due to reduced luminous[40] efficiency and increased atmospheric attenuation in this
wavelength, the visibility is reduced even further. By comparing the differences be-
tween the ionic and atomic spectrum for barium or strontium, as shown in Appendix I,
the reader can readily visualize the color (wavelength) shift. No ionic spectrum was
given in Appendix I for sodium or the other Group I alkali metals. These ionic spectra,
as indicated earlier, would be expected to resemble the atomic spectra of the inert
gases with a shift toward the ultraviolet. In any event, a strong, distinct, desirable
color would not be expected from ionized alkali metals such as are emitted by their
neutral atoms as atomic spectra.
5. Ionization in flames has been studied very extensively. The reader is referred to Gay-
don,[24] Sugden[25,32,37] and others[26,38] for additional information concerning such ioniza-
tion.
g. Ionization Buffer

Page 8 Theory of Colored Flame Production — Douda

 1. Occurrence of ionization of metal vapors, especially the alkali metals, strontium and bar-
ium, has already been described. Ionization of barium has already been described. Ioniza-
tion of barium in a barium-based flame has been described as being particularly detrimen-
tal to emission of the desired green color. One means for reducing ionization is to reduce
the temperature. This relationship was previously described. From a practical standpoint,
to reduce the operating temperature to the point that ionization of barium would be negli-
gible may result in an unserviceable pyrotechnic for reasons other than color. It is, there-
fore, desirable to be able to suppress barium ionization by means other than temperature
reduction. This can be accomplished[8] by the addition of an easily ionized metal to the
flame. In Military Pyrotechnics, potassium, usually in the form of the perchlorate, is used
to buffer the ionization. The selection of the perchlorate salt of potassium instead, for ex-
ample, the nitrate salt, is to provide not only the buffer effect and oxygen supply but also a
halogen supply. Halogen influences will be discussed separately.
2. Continuing with the ionization buffer discussion, the ionization of barium can be de-
scribed as:
Baº R Ba+ + e–
Potassium, which is even more readily ionizable than barium, can be described in a similar
manner:
Kº R K+ + e–
If conditions which approach equilibrium are assumed, then by Le Chatelier’s Law of
Mass Action, the electrons readily produced by the potassium ionization will bring stress
to bear on the barium equilibrium, thereby displacing the barium reaction toward the neu-
tral atom. In so doing, less barium is ionized leaving more barium to emit its atomic spec-
trum or to form a compound that will emit its band spectrum.
3. The effect of potassium on color should be noted. The ionized potassium will emit a spec-
trum that resembles the atomic spectrum for argon whose strongest lines are in the deep
red and near infrared. As seen from the thermodynamic properties listed in Appendix II,
except for the halogen salts, potassium will exist as the neutral atom in flames over 2000
K and, therefore, will emit the characteristic purplish-red and bluish-purple atomic lines
listed in Appendix I. Flame emission spectra for the potassium-halogen salts could not be
located. The ionic and atomic potassium spectra will not cause appreciable interference in
a strontium-red flame. Somewhat more interference would be expected in a barium-green
flame. Fortunately, however, the benefits of the ionic buffering action outweigh the disad-
vantage of the off-color ionic and atomic spectral emissions.
h. Halogen Influences and Color Production
1. Long ago, pyrotechnicians started to add halogens, in some form, to pyrotechnic composi-
tions in order to intensify or enhance the color. Chlorine in the form of a perchlorate salt is
frequently used for this purpose. In addition, non-oxidizing chlorinated additives such as
hexachlorobenzene and polyvinyl chloride are also used. Although the effect is known, the
mechanism is not completely understood.
a) Barium-Strontium
1) Ellern[14] credited Hart as referring to the red flame as due to molecular bands in
the red region, caused by molecular strontium oxide and chloride, and diluted with
other lines and bands from incandescent particles. Hart also referred to the green
flame as being due to bright blue bands from copper and barium chloride in the
4000–5000 and 5000–5500 Å region. More recent information leads to a slightly
different explanation.

Theory of Colored Flame Production — Douda Page 9

 2) Colored flame pyrotechnic compositions contain organic binders and chlorinated
organic molecules. The combustion (oxidation) of these organic molecules pro-
vides the flame gases with a source of atomic and molecular hydrogen, neutral and
negatively charged hydroxyl radicals, atomic and anionic chlorine and other
materials. The low, 57 kcal/mole, dissociation energy of molecular chlorine as
shown in Appendix II leads to the absence of molecular chlorine from the flame.
Using barium as the example metal, several combinations can be expected.
Cl+H+OH R HCl+OH
OH+Ba R BaOH
Cl+Ba R BaCl
The combination of chlorine and hydrogen to form hydrochloric acid is spontane-
ous at 2000 K since the free energy of formation is –25.5 kcal/mole. Once formed,
the HCl can be expected to be stable at temperatures in reasonable excess of 2000
K since the dissociation energy is about 103 kcal/mole. The high likelihood of
HCl formation plus the stability after formation causes an excess of the OH radi-
cal. This excess, in turn, represses the diatomic metal chloride, BaCl formation
and increases the triatomic metal hydroxide, BaOH, formation. Another consid-
eration with respect to the suppression of the BaCl formation is the low,
51 kcal/mole, dissociation energy of the diatomic chloride. Enhancement, there-
fore, results by shifting the equilibrium toward the formation of BaOH that, as
shown in Appendix II, emits in the green wavelength. Pyrotechnicians prefer
BaOH formation to BaO formation because the BaO band spectrum encompasses
many undesirable wavelengths. BaO would probably form in greater quantities if
the BaOH formation were not promoted by the equilibrium shift caused by the
chlorine addition. As a consequence, if BaOH formation is increased at the ex-
pense of BaO, this, in itself, will result in a more desirable or enhanced color.
3. Halogen enhancement of strontium is analogous to that described for barium. In both in-
stances, because the pyrotechnic compositions are usually saturated with the metal and
halogen, a very substantial amount of the metal halide will be present in the flame in addi-
tion to the hydroxide. The halide formation with barium and strontium is not objectionable
because these molecules fortunately also emit energy as defined by their molecular band
spectrum in the desired wavelength.
b) Alkali Metals
1) The halogen effect with respect to the alkali metals is different from that just de-
scribed for barium and strontium. Generally, because the desirable emission from
the alkali metals is the atomic spectrum of the neutral atoms, the addition of a
halogen will not result in enhancement. The desired emission of the atomic spec-
trum will be substantially reduced because of salt formation.
2) All the alkali metals will not behave identically because of the stability differences
in their hydroxide. Sugden[37] points out that at 2245 K, LiOH is very stable
whereas NaOH is so unstable as to be effectively absent from the flame. Among
the alkali metals, the stability in decreasing order is
LiOH > CsOH > RbOH > KOH > NaOH
In a manner similar to that used for barium and strontium, and using rubidium as
the example metal, several combinations can be expected

Page 10 Theory of Colored Flame Production — Douda

 Cl+H+OH R HCl+OH
Cl+Rb R RbCl
HCl+Rb R RbCl+H
OH+Rb R RbOH
The equilibrium of the last equation will shift considerably for different alkali
metals because of the previously mentioned stability differences. The variation in
this equilibrium will affect the quantity of halogen salt formed. Sodium will form
NaCl with little or no NaOH formation, whereas lithium will form LiOH and a
significant amount of LiCl. In any event, whether it be hydroxide or halide forma-
tion, the formation of any alkali metal compound will reduce the amount of alkali
metal neutral atoms available to radiate their atomic spectrum. Because halides
stimulate alkali metal compound formation, the halogens must be classed as nega-
tive enhancement agents in flames containing alkali metals. In contrast, halogens
are positive enhancement agents in flames containing the alkaline earth metals be-
cause, under those conditions, the hydroxide and halide band spectra are preferred
over the atomic spectrum.
c) Boron
1) When boron is added to a flame, the green color that results is due predominantly
to BO2. Some BO is probably also formed which emits mostly in the blue to ultra-
violet. From thermodynamic data listed in Appendix II, it is concluded that the
boron oxides are not only very likely to form (ΔFHigh) but also very stable (High
dissociation energy). Except for iodine, the boron halides also are identified with
high free energy of formation and dissociation energy. If the halide band spectrum
were predominantly green in nature, the addition of a halide would be beneficial.
On the contrary, however, BF has an undesirable yellow system and BBr and BCl
emit primarily in near ultraviolet. If, therefore, a halogen other than iodine were
introduced, a stable halide would form. This, in turn, would reduce the amount of
the oxide present that was radiating in the beneficial green wavelengths. The net
result would be a shift toward blue with a negative enhancement with respect to
green.
d) Thallium
1) The great bulk of the thallium[11] in a flame is present as the free element. The
green flame color is, therefore, due to the neutral atom atomic spectrum. Oxide
and hydroxide formation do not occur in the flame to any appreciable degree. The
more electronegative halogens will form reasonably stable halides in the flame.
These can be expected to emit band spectra. Thallium fluoride, chloride and bro-
mide emit in the deep blue to near ultraviolet wavelength. These emissions are of
no particular value for green flame production. Thus, when a halogen is intro-
duced, some stable halide forms. This in turn reduces the amount of the neutral
atoms that are radiating in the desired green lines. The net result is a shift toward
blue with a negative enhancement with respect to green.
e) Copper
1) The great bulk of the copper[36] in a flame is present as the free atom with not
more than 10% as CuO. Appendix I shows an undesirable band spectrum for CuO
in the orange region and weak bands in the green region. The free copper atoms
emit a weak green line at ~5l05Å. The composite of these emissions would indi-
cate a weak polluted greenish color. Contrary to this, copper, when introduced
into a flame, exhibits a strong yellowish green color. This is attributed to CuOH

Theory of Colored Flame Production — Douda Page 11

 molecular emission. Note that CuOH formation is recognized even in the absence
of halogens. In limited amounts, this is true also of barium, strontium and lithium.
2) During the discussion of the other metals, thermally stable salt formation was de-
scribed as a result of halogen addition. Appendix II shows generally low dissocia-
tion energies for copper compounds. This accounts for the flame composition be-
ing predominantly free copper. When halogens are added to a copper flame, the
color changes from green to blue. By the postulates laid down for barium and
strontium, the addition of halogen to a copper flame would be expected to form
the halide acid causing excess OH that, in turn, would combine with the metal to
enhance the color emission by radiating the band spectrum. Because of the low
dissociation energy, the halide salt would not be expected to form in large
amounts. This explanation based on thermal considerations and room temperature
theory does not appear to hold true for copper. This is obvious because blue color
results instead of an enhanced green.
3) What appears to be a serious flaw in the argument is, in fact, support for the the-
ory of chemiluminescence and is readily explained without deviation from the ba-
sic argument. When halogen is added to a flame containing copper, a small
amount of the copper halide salt will form. A small amount (as contrasted to large)
is formed because of the low dissociation energy. Thus the equilibrium favors
dissociation. The small amount of halide salt formed emits a blue band spectrum.
This emission dominates that of the CuOH emission that leads to the conclusion
that CuOH is probably present in an extremely small quantity. As in the case of
barium and strontium, the halogen combines with hydrogen to form the halide
acid, thereby causing an OH excess which, in turn, contributes to formation of
more CuOH. Also, as in the case of barium and strontium, although more metal
hydroxide is formed, the metal halide is formed in even greater amounts. Because
the strontium and barium metal halides emit in desirable wavelengths, the net re-
sult is a quantitative increase of emission in desirable wavelengths. In the case of
copper, however, the increase in CuOH is outweighed by the increase in copper
halide formation, thus resulting in a shift from CuOH green emission to blue cop-
per halide emission.
4) The preceding discussion was based on thermal considerations. Gaydon,[19] in dis-
cussing carbon monoxide flames, suggested a catalytic effect that should be con-
sidered in addition to thermal possibilities. He stated, “Another persistent impurity
in the spectra of CO flames is CuCl. These bands are strongest in the blue and
blue-green and are degraded to the red. The reason why these bands occur so
readily in CO but not other flames is something of a mystery; it is possible that
CuCl acts as a catalyst in the oxidation and receives excitation energy from the
process”.
f) Metal Halide Molecule Excitation
1) Dean[5] states that the halide radical will tend to lessen the attraction of the elec-
tron to the nucleus and thus render easier the excitation process. This feature is of
importance particularly in flames containing barium or strontium. In these flames
a major part of the color is due to molecular excitation and a significant portion of
the emitting molecules are the halide salt. The fact that the excitation process is
made easier by the halide leads to a net increase in emission. This increase is also
considered to be halide enhancement.
g) Halogen Selection

Page 12 Theory of Colored Flame Production — Douda

 1) The color of pyrotechnic flames is dependent on the volatile material in the flame.
This material may be the neutral atom, a diatomic or polyatomic molecule or ions.
Color then is dependent on the ability to keep the material volatilized within the
flame. The ability to keep material volatilized within the flame is, among other
things, related to its boiling point and heat of fusion. It is logical to conclude that,
for a flame with a given amount of energy, the amount of the material in the flame
is a decreasing function of its boiling point. Thus a low boiling point favors a lar-
ger quantity of volatilized matter in the flame.
2) It has already been established that halogens are added to pyrotechnic colored
flare compositions to benefit from their enhancement effect. When the metal hal-
ide is used as an emitter, it is desirable to keep it volatilized. Since the more elec-
tronegative halogens form salts with higher boiling points, the electronegativity of
the halogen will be related to the quantity of halide salt which a flame can keep
volatilized. The halogen electronegativity scale is:
F > Cl > Br > I
The complete electronegativity scale of the elements has been tabulated by
Pauling.[28] Without considering other factors, iodine would be the best choice to
provide a low boiling material. See Appendix II for a listing of melting and boil-
ing points. Some iodides are, however, unstable at the flame temperature. A more
electronegative halogen must, therefore, be selected. Another important considera-
tion is the band spectrum that the metal halide will omit. These band spectra are
described in Appendix I. Although, for example, a metal iodide is stable, its spec-
trum may not be beneficial to the desired color. In this instance, a compromise
will probably result. A more electronegative halogen with a higher boiling point
will probably be selected in order to obtain a preferred spectrum. The selection of
the halogen, therefore, is not an arbitrary matter. Consideration must be given to
such factors as stability, spectrum and boiling point of its salt.
3) Composite flame spectra for copper, barium and strontium are included in Appen-
dix I. These hypothetical spectra would only exist if all of the halogens were pre-
sent in the flame simultaneously. Such a condition would have no practical advan-
tage. They were included, however, to illustrate wavelength shifts that can be ex-
pected by halogen variation.
i). Chemiluminescence
1) Chemiluminescence was discussed briefly in the Spectrum vs. Emitter Section.
This phenomenon was also mentioned in the description of copper color produc-
tion. The characteristic of C-Type chemiluminescence that is of particular impor-
tance is the ability of a small number of molecules to emit an abnormally large
amount of radiation. The effect is remarkable. BaO has a dissociation energy of
124 kcal/mole and BaOH is estimated to have a dissociation energy (into Ba and
OH) of less than 60 kcal/mole. Sugden[36] based on that data estimated the ratio of
BaO:Ba:BaOH in a typical flame to be roughly l03:l:l0–3. It, therefore, is remark-
able that such a small quantity of BaOH will emit such an intense green color. C-
Type chemiluminescence is, therefore, suggested.
2) It is emphasized that C-Type chemiluminescence results from the formation of an
excited molecule directly in the excited state in amounts bearing little or no rela-
tion to the ground-state concentrations. The molecular emissions are probably due
to molecules that have no independent existence outside the flame. The phenome-
non is not a thermal type excitation and, therefore, must be considered as a radia-
tion source in addition to thermal radiations. The strong strontium red, barium

Theory of Colored Flame Production — Douda Page 13

 green and copper green colors in a flame have been attributed primarily to C-Type
chemiluminescence of SrOH, BaOH and CuOH.
j) Emission Suppression and Intensification
1) Pyrotechnicians empirically learned to avoid the use of various compounds in
colored flame compositions. When used, serious degeneration of the color often
results. Emission suppression of alkaline earth radiations is caused by elements[7]
such as aluminum, boron, chromium, phosphorus, silicon, iron, beryllium and sul-
fur. The suppression appears to be based on the formation of molecular com-
pounds with the alkaline earth metals which are either difficult to evaporate or dif-
ficult to dissociate. Many of the suppressors possess the ability to form anions
such as the aluminates, borates, phosphates, chromates and sulfates. This phe-
nomenon may be one of the reasons pyrotechnicians have been unable to color the
flame from standard day-night type phosphorus compositions.
2) The red burning railroad "fusee” is shown by Ellern[17] to contain 10% sulfur. Sul-
fur is described along with other materials as having desirable properties from the
viewpoint of being slow and cool burning. These references to successful com-
mercial use in a colored flame composition and to its desirable properties empha-
size that an element or its compound may be used to advantage when the suppres-
sion properties are outweighed by desirable thermodynamic, chemical and physi-
cal properties. When ultimate performance is required, the use of any of the listed
suppressors should be considered very carefully.
3) Although the oxalate anion is reported[9] to seriously repress sodium emission, so-
dium oxalate is frequently used as a sodium donor in yellow flame formulations.
From a practical standpoint, the suppression can frequently be tolerated because of
the extremely high intensity of the sodium atomic lines. The oxalate ion does not
appear to seriously suppress strontium or barium emission.
4.) Phosphates and sulfates strongly inhibit the emissions of most metals although
sulfate has been reported[10] as an intensifier of boron emission. The acetate anion
is generally considered to be an intensifier. This suggests that for yellow flames,
sodium acetate may be better than sodium oxalate. For that matter, some benefits
may be realized from using strontium or barium acetate instead of their oxalates.
k) Flame Equilibria
1) Throughout the discussions, molecule formations, dissociations, ionization and
similar events were described by indicating whether or not the event would take
place. Since most of the reactions in the flame are reversible, an equilibrium for
each event must be considered. For example, because of incomplete combustion
and turbulence, there is departure from equilibrium within the flame.
2) A quasi-equilibrium is probably established between the reactants and reaction
products. In addition, there are temperature gradients within the flame which tend
to upset established equilibria. It would be an advantage to describe each occur-
rence in a flame with an equilibrium constant. Under given and constant flame
conditions, it would then be possible, for example, to calculate the quantity of a
reactant or reaction product in the flame. Because, however, of departure from
equilibrium, temperature gradients, turbulence, incomplete knowledge of existing
reactions in the flame and other causes of variability, absolute statements of quan-
tity were not used to describe events within the flame.
3) When it was stated that an event would or would not occur, the reader must rec-
ognize that these judgments are not absolute with respect to quantity. In addition,

Page 14 Theory of Colored Flame Production — Douda

 many events were described using relative quantity descriptions. In most in-
stances, the assessment was made based on thermodynamic properties of the ma-
terials involved. For example, it was stated that the low, 57 kcal/mole dissociation
energy of molecular chlorine leads to its absence from the flame. This statement
was made because of the relatively large separation between the 57 kcal/mole dis-
sociation energy and the energy of a 2000 K flame that was nominally equated to
85 kcal/mole. If the dissociation energy of Cl2 had been even lower, an even
smaller amount of Cl2 would form. Conversely, the more the dissociation energy
is larger than the nominal flame energy, the more likely it is that the flame will not
dissociate the material, thereby allowing more of the material to be present in the
flame. It is in such a relative manner that each event’s occurrence was described.

4. Postulates and Summary

a. An ideally formulated pyrotechnic colored flame composition is one which, when burned,
produces combustion products all of which readily emit radiation in the wavelength of the de-
sired color. The preferred emitters of various elements are:

Preferred Emitters of Various Elements.

Element Combustion Product Flame Color

Lithium Liº red

Sodium Naº yellow
Rubidium Rbº red
Cesium Csº blue
Barium BaX, BaOH green
Strontium SrX, SrOH red
Boron BO2 green
Thallium Tlº green
Copper Cuº and CuOH green CuX blue

X = halogen

Ionized potassium, rubidium and cesium are useful ionization buffers. To prepare efficient
formulations, pyrotechnics must be compounded to form the neutral atoms or molecules in
large amounts. To do this, the approach will vary with the element used to produce the color.
Certain postulates apply which disregard all practical material considerations, such as sensitiv-
ity, stability, hygroscopicity, combustion properties, cost and toxicity. Such postulates that
apply only to the production of color in a flame are:
1. Formulate the composition so that a maximum amount of the preferred emitter is produced
in the flame as a vapor.
2. Adjust the flame operating temperature in relation to the production of the maximum
amount of excited emitter. This requires that the temperature be kept low to reduce ioniza-
tion and that it be kept high enough to produce vaporization and excitation of preferred
species and dissociation of unwanted molecules.
3. Use an ionization buffer to aid in ionization suppression. This is of particular advantage
when the color is the result of the alkali or alkaline earth metals.

Theory of Colored Flame Production — Douda Page 15

 4. For elements whose color depends on the neutral atom, avoid the addition of materials
whose elements can combine with the neutral atoms to form molecules. For the remaining
elements, add materials whose elements will combine to form the preferred molecules.
5. Formulate to benefit from chemiluminescence and enhancement effects.
6. Select materials to reduce emission suppression that results from many anions and numer-
ous metals.
7. Do not introduce material that is not essential to the production of color. This will reduce
unwanted emissions and background radiation.
b. With consideration only to color production, it is concluded that simultaneous compliance
with all the postulates is impossible. This reason alone makes compromise mandatory. When
considerations related to practicality are introduced, additional concessions result. It is, there-
fore, fortunate for the author that the purpose of this presentation is to describe only the theory
of colored flame production. Thus, it is not necessary to list flare formulae that will produce
colored flames under all conceivable conditions and in fulfillment of all requirements. A better
understanding of the chemical and physical processes involved in colored flame production
will, however, enable the preparation of compositions in a more rational manner. It was for
this purpose that the theories and attributes associated with colored flame production were dis-
cussed and enumerated.

References
1) J. A. Dean, Flame Photometry, McGraw Hill, New York (1960) p 17.
2) Ibid., p 31.
3) Ibid., p 33.
4) Ibid., p 36.
5) Ibid., p 37.
6) Ibid., p 42.
7) Ibid., pp 41 and 107.
8) Ibid., p 104.
9) Ibid., p 166.
10) Ibid., pp 229–230.
11) Ibid., p 236.
12) J. Drowart and P. Goldfinger, Annual Review of Physical Chemistry, Annual Reviews, Inc., Palo
Alto, CA, Vol. 13 (1962) p 459.
13) H. Ellern, Modern Pyrotechnics, Chemical Publishing Co., Inc., New York (1961) p 78.
14) Ibid., p 81.
15) Ibid., p 90.
16) Ibid., p 96.
17) Ibid., pp 97 and 275.
18) A. G. Gaydon, The Spectroscopy of Flames, John Wiley, New York (1957) pp 48–72.
19) Ibid., p 92.

Page 16 Theory of Colored Flame Production — Douda

20) Ibid., p 195.
21) A. G. Gaydon, Dissociation Energies and Spectra of Diatomic Molecules, Chapman and Hall,
London (1953) p 3.
22) A. G. Gaydon and H. G. Wolfhard, Flames; Their Structure, Radiation and Temperature, Chap-
man and Hall, London (1960) p 226.
23) Ibid., pp 234–301.
24) Ibid., pp 302–323.
25) J. A. Green and T. M. Sugden, Ninth Symposium (International) on Combustion, Academic Press,
New York (1963) pp 607–621.
26) S. A. Greene, A Literature Survey of Ions in Flames, Aerospace Corporation Report No. TDR-
169 (S3153-0l)TN-5, Contract No. AF-04(695)-169, 15 June 1963. See NTIS AD410329.
27) L. Pauling, The Nature of the Chemical Bond And the Structure of Molecules and Crystals, Cor-
nell University Press, Ithaca, NY (1960) p 57.
28) Ibid., p 93.
29) Ibid., pp 594–601.
30) Ibid., p 622.
31) P. J. Padley and T. M. Sugden, Seventh Symposium (International) on Combustion, Butterworths
Scientific Publications, London (1959) pp 235–244.
32) P. J. Padley and T. M. Sugden, Eighth Symposium (International) on Combustion, Williams and
Wilkins, Baltimore (1962) pp 164–179.
33) C. F. Prutton and S. H. Maron, Fundamental Principles of Physical Chemistry, Macmillan, New
York (1956) p 296.
34) C. F. Prutton and S. H. Maron, Fundamental Principles of Physical Chemistry, Macmillan Co.,
NY (1956) p 318.
35) Ibid., p 331.
36) T. M. Sugden, Annual Review of Physical Chemistry, Annual Reviews, Inc., Palo Alto, CA, Vol.
13 (1962) pp 381–382.
37) T. M. Sugden, Fifth Symposium (International) on Combustion, Reinhold Publishing, NY (1955)
pp 406–408.
38) A. Van Tiggelen, Ion Production and Concentration in Flames, University of Louvain (Belgium),
Annual Summary Report No. 2, Contract no. AF-61(052)-398, May 1962. See NTIS AD278417.

39) Unknown, International Encyclopedia of Chemical Science, D. Van Nostrand Co., Inc., NY
(1964).
40) Unknown, The Science of Color, Thomas Y. Crowell Co., NY (1954) pp 227 and 308.

Appendix I

1. Contents
a. Spectra

Theory of Colored Flame Production — Douda Page 17

 Lithium
Sodium
Potassium
Rubidium
Cesium
Thallium
Barium
Strontium
Boron
Copper
b. Chromaticity Data Diagram

2. Symbols
λ = wavelength in Angstroms (Å)
I = relative intensity
εν = electron volts
Å = Angstrom
mµ = millimicron = l0 Å

3. References
a) J. A. Dean, Flame Photometry, McGraw-Hill, New York, 1960.
b) A. G. Gaydon, The Spectroscopy of Flames, John Wiley, New York, 1957.
c) P. T. Gilbert, Flame Spectra of the Elements, Bulletin 753-A, Beckman Instruments, Inc., Fuller-
ton, CA, 1961.
d) G. R. Harrison, Massachusetts Institute of Technology Wavelength Tables, John Wiley, New
York, 1956.
e) L. Pauling, The Nature of the Chemical Bond, Cornell University Press, Ithaca, NY, 1960.
f) R. W. B. Pearse and A. G. Gaydon, The Identification of Molecular Spectra, John Wiley, New
York, 1963.

4. Discussion of Contents
a. The atomic and ionic spectra were selected from the MIT Wavelength Tables.[d] The elemental
ionization potentials were calculated from the energies listed in Table 2–5 in Pauling.[e] The
electron volt, εν, entry listed with the atomic and ionic spectra is the excitation potential or
energy required to excite that particular line. These energy levels were selected from the MIT
Tables. The band spectra were collected from Pearse,[f] Dean,[a] Gaydon[b] and Gilbert.[c] Data
concerning continuum were selected from Gaydon and Dean.
b. The intensities, I, are eye estimates based on a scale of 10 for the strongest line or band in the
system. Because the values were collected from several sources, the values are very unreliable

Page 18 Theory of Colored Flame Production — Douda

 and should not be used for any quantitative purposes. For that matter, they are even unreliable
for qualitative purposes.
c. Composite flame spectra were prepared for barium, strontium and copper. Flames will proba-
bly never correspond to these composites since all halogens will undoubtedly never be present
in one pyrotechnic composition. The information was, however, collected into its composite
form so that by viewing one page, the reader can visualize the location of various molecules
with respect to the wavelength and color that they emit and in relation to one another. These
composite spectra do not include continuum or band emissions from molecular and free radi-
cal products of combustion from organic compounds.
d. All emissions for a specific element or molecule are not listed in this collection. Only the more
intense and persistent lines and bands have been mentioned. For example, 175 lines are listed
for sodium in the MIT Wavelength Tables whereas only six are listed herein. For extensive
listings of emission data, the MIT Wavelength Tables and similar documents must be con-
sulted.
e. A Chromaticity Data diagram that relates wavelength to color was included to aid the reader to
visualize the color in relation to various radiation wavelengths.

Lithium
Elemental Lithium Ionization Potential 5.39 εν
Atomic Spectrum
λ εν I Ionic Spectrum
6707.8 1.8 10 (None Located)
6103.6 3.9 5
4603.0 4.5 4 Continuum 460 to 320 mµ
3232.6 3.8 3

Sodium
Elemental Sodium Ionization Potential 5.14 εν
Atomic Spectrum
λ εν I Ionic Spectrum
5895.9 2.1 9 (None Located)
5889.9 2.1 10
5688.2 4.3 — Continuum 602 to 360 mµ
5682.7 4.3 —
3303.0 3.7 4
3302.3 3.7 4

Theory of Colored Flame Production — Douda Page 19

 Potassium
Elemental Potassium Ionization Potential 4.34 εν
Atomic Spectrum
λ εν I Ionic Spectrum
7699.0 1.6 9 (None Located)
7664.9 1.6 10
4047.2 3.0 4 Continuum 570 to 340 mµ
4044.1 3.1 5

Rubidium
Elemental Rubidium Ionization Potential 4.18 εν
Atomic Spectrum
λ εν I Ionic Spectrum
7947.6 1.6 10 (None Located)
7800.2 1.6 10
6298.6 — 5
4215.6 2.9 8
4201.9 2.9 8

Cesium
Elemental Cesium Ionization Potential 3.89 εν
Atomic Spectrum
λ εν I Ionic Spectrum
8943.5 1.4 10 (None Located)
8521.1 1.4 10
4593.2 2.7 7
4555.4 2.7 8

Thallium
Elemental Thallium Ionization Potential 6.11 εν
Atomic Spectrum
λ εν I
5350.5 3.3 10
3775.7 3.3 9
3519.2 4.5 7
3229.8 4.8
2918.3 5.2 2
2767.9 4.5 2

Page 20 Theory of Colored Flame Production — Douda

 Barium
1. Elemental Barium
Elemental Barium Ionization Potential 5.21 εν
Atomic Spectrum Ionic Spectrum
λ εν I λ εν I
5777.7 3.8 9 4934.1 7.7 4
5535.6 2.2 10 4554.0 7.9 10
5519.1 3.8 6 4130.7 10.9 0.5
5424.6 3.8 1 3891.8 10.9 0.2
3071.6 4.0 1 2335.3 11.2 0.6

2. BaOH Band Spectrum

Green bands, maxima 487, 512, 515 and 527 mµ

3. BaO Band Spectrum

λ I λ I λ I
7097.4 5 6039.6 9 5349.7 8
6782.8 8 5976.3 3 5214.7 7
6493.1 9 5864.5 10 5086.7 6
6291.0 8 5805.1 6 4965.4 3
6224.7 6 5701.0 8 4850.6 6
6165.1 6 5644.1 9 4680.3 5
6102.3 5 5492.7 10

4. Barium Oxide (emitter species uncertain)

Band groups at 4800, 5020 and 5500 Å. The 5500 group shows two main bands at 5445–5452
and 5482–5488. Band heads have been observed from 4730 to 4855 and from 5007 to 5018.
5. BaBr Band Spectrum
λ I λ I
5415.9 4 5260.6 4
5360.1 10 5208.2 10
5305.5 6 5156.4 5

6. BaCl Band Spectrum

λ I λ I
5320.8 1 5139.2 \
10
5240.5 10 5136 /
5213 1 5066 1
5167 2

Theory of Colored Flame Production — Douda Page 21

 7. BaF Band Spectrum
Green System
λ I
5000.6 8
4992.1 5
4950.8 10

Extreme Red System

λ I λ I
7430.8 7 6958.7 6
7142.0 10 6935.1 6
7119.2 10

8. BaI Band Spectrum

λ I
5609.5 10
5381.7 7
5260 —
5160 —

9. Barium Composite Flame Spectrum

λ I Species λ I Species λ I Species
7430.8 7 BaF 5644.1 9 BaO 5208.2 10 BaBr
7142.0 10 BaF 5609.5 10 BaI 5167 2 BaCl
7119.2 10 BaF 5535.6 10 Ba 5160 — BaI
7097.4 5 BaO 5519.1 2 Ba 5156.4 5 BaBr
6958.7 6 BaF 5492.7 10 BaO 5150 — BaOH
6935.1 6 BaF 5424.6 1 Ba 5139.2 \
10 BaCl
6782.8 8 BaO 5415.9 4 BaBr 5136 /
6493.1 9 BaO 5381.7 7 BaI 5120 — BaOH
6291.0 8 BaO 5360.1 10 BaBr 5086.7 6 BaO
6224.7 6 BaO 5349.7 5 BaO 5066 1 BaCl
6165.1 6 BaO 5320.8 3 BaCl 5000.6 8 BaF
6102.3 5 BaO 5305.5 6 BaBr 4992.1 5 BaF
6039.6 9 BaO 5270 — BaOH 4965.4 3 BaO
5976.3 3 BaO 5260.6 4 BaBr 4950.8 10 BaF
5864.5 10 BaO 5260 — BaI 4934.1 4 Ba+
5805.1 6 BaO 5240.5 1 BaCl 4870 — BaOH
5777.7 5 Ba 5214.7 7 BaO 4850.6 6 BaO
5701.0 8 BaO 5213 1 BaCl 4680.3 5 BaO
4554.0 10 Ba+

Page 22 Theory of Colored Flame Production — Douda

 Strontium
1. Elemental Strontium
Elemental Strontium Ionization Potential 5.69 εν
Atomic Spectrum Ionic Spectrum
λ εν I λ εν I
4962.3 4.3 3 4305.5 11.6 0.4
4872.5 4.3 2 4215.5 8.6 3
4832.1 4.3 5 4077.7 8.7 4
4607.3 2.7 10 3474.9 12.2 0.8
3464.6 12.2 2
3380.7 12.2 1.5

2. SrBr Band Spectrum

λ I
6666.7 10 (Has a weak violet system)
6513.0 10

3. SrCl Band Spectrum

λ I λ I
6755.6 3 6482.9 4
6744.7 5 6362.4 5
6619.9 5 6358.7 10
6613.7 10 6239.3 2

4. SrF Band Spectrum

λ I λ I λ
6655.6 7 6419.0 \ 5779.5
8
6632.7 10 6394.7 / 5772.0
6527.6 7 6306.1 \ 5622 to 5670
8
6512.0 10 6283.1 /

5. SrI Band Spectrum

λ I λ I
7094.0 2 6767.8 10
7011.0 10 6691.5 8
6930.2 10 6662.3 8
6847.7 10 6177.3 4

6. SrOH Band Spectrum

λ λ λ I
6820 6114.2 6109.6 1
6675 6111.8 6101.1 3
6590 6109.8 6095.9 4
6460 6107.9 6089.9 6
6107.5 6084.7 10
6105.2 6076.6 8
6050 Strong

Theory of Colored Flame Production — Douda Page 23

 7. Sr2O2 Band Spectrum
λ
5950
5969

8. Strontium Composite Flame Spectrum

λ I Species λ I Species λ I Species
7094.0 2 SrI 6527.6 7 SrF 6107.9 — SrOH
7011.0 10 SrI 6513.0 10 SrBr 6107.5 — SrOH
6930.2 10 SrI 6512.0 10 SrF 6105.2 — SrOH
6847.7 10 SrI 6482.9 4 SrCl 6095.9 4 SrOH
6820 — SrOH 6460 — SrOH 6089.9 6 SrOH
6767.8 10 SrI 6419.0\ 6084.7 10 SrOH
8 SrF
6755.6 3 SrCl 6394.7/ 6076.6 8 SrOH
6744.7 5 SrCl 6362.4 5 SrCl 6050 — SrOH
6691.5 8 SrI 6358.7 10 SrCl 5779.5 — SrF
6675 — SrOH 6306.1\ 5772.0 — SrF
8 SrF
6666.7 10 SrBr 6283.1/ 5622 \
— SrF
6662.3 8 SrI 6239.3 2 SrCl 5670 /
6655.6 7 SrF 6177.3 4 SrI 4962.3 3 Sr
6632.7 10 SrF 6114.2 — SrOH 4872.5 2 Sr
6619.9 5 SrCl 6111.8 — SrOH 4832.1 5 Sr
6613.7 10 SrCl 6109.8 — SrOH 4607.3 10 Sr
6590 — SrOH 6109.6 1 SrOH

Boron
1. Elemental Boron
Elemental Boron Ionization Potential 8.29 εν
Atomic Spectrum Ionic Spectrum
λ εν I λ εν I
2497.7 4.9 5 3451.4 20.9 0.05
2496.8 4.9 4

2. BF (may be BF2 or BF3) Band Spectrum

Yellow System
λ I λ I λ I
5993.8 8 5822.1 10 5803.8 6
5984.4 6 5815.1 8 5664.0 6
5825.7 7 5807.3 6

Blue Green System

λ I λ I λ I
5470.8 6 5456.8 8 4461.4 6
5460.1 4 4464.9 6 4443.5 6

Page 24 Theory of Colored Flame Production — Douda

 3. BO2 Band Spectrum
λ I λ I λ I
6200 5 5450 9 4710 3
6030 7 5180 8 4520 1
5800 7 4930 5

Copper
1. Elemental Copper
Elemental Copper Ionization Potential 7.73 εν
Atomic Spectrum Ionic Spectrum εν
λ εν I λ εν
5220.1 — 4
5218.2 6.2 5 2247.0 15.9
5153.2 6.2 4 2192.3 16.2
5105.5 3.8 4 2136.0 16.2
3274.0 3.8 9
3247.5 3.8 10

2. CuBr Band Spectrum

λ I λ I λ I
5032.2 3 4883.4 4 4810.4 2
4954.7 4 4879.3 8 4341.1 10
4288.6 7

3. CuCl Band Spectrum

λ I λ I λ I
5262.3 6 4881.5 4 4515.9 5
5152 3 4846.9 3 4433.8 9
4982.2 2 4788.5 2 4353.9 10
4946.1 1 4755.7 1 4280.9 9
There are additional bands toward the ultraviolet.
4. CuI Band Spectrum
λ I λ I λ I
5494.1 3 5312.4 5 5117.3 3
5477.1 4 5297.5 6 5101.9 3
5461.3 3 5283.8 4 5072.8 10
5402.2 5 5241.0 3 5034.6 3
5486.5 6 5226.1 5 5019.7 7
5371.5 5 5212.2 7 4983.9 4
5357.4 3 5155.8 3 4968.3 5
5328.5 3 5141.1 7 4919.1 3
Additional bands exist toward the ultraviolet.

Theory of Colored Flame Production — Douda Page 25

 5. Orange Region: CuO Band Spectrum
λ I λ I λ I
6547 — 6376.9 2 6059.3 10
6530 — 6294.0 5 6045.1 9
6493.4 1 6280.9 1 5847.6 3
6430.0 3 6161.5 9 5832.7 2
6400.4 5 6146.8 8 5827.7 1

Green Region: Large number of weak bands, including a little group of heads be-
tween 5237 and 5228 Å, and heads at 5344, 5313, 5308, 5279 and 5274 Å. Emitter
uncertain.

6. CuOH Band Spectrum

Strong diffuse band in green at 5350 to 5550 Å and a weaker band in the orange-red at 6150 to
6250 Å. Wide bands have also been reported at 505 and 524 mµ.

7. CuF Band Spectrum

λ I λ I λ I
5694.3 6 5086.4 2 4932.0 8
5685.7 6 5061.1 7 4926.8 6
5677.2 5 5052.3 6 4901.3 5
4781.9 4

8. CuH Band System at 4280 Å.

9. Copper Composite Persistent Flame Spectrum

λ I Species λ I Species λ I Species

6400.4 5 CuO 5312.4 5 CuI 5052.3 6 CuF
6294.0 5 CuO 5308 — CuO 5050 — CuOH
6250 \ 5297.5 4 CuI 5019.7 7 CuI
— CuOH
6150 / 5283.8 6 CuI 4983.9 4 CuI
6161.5 9 CuO 5279 — CuO 4968.3 5 CuI
6146.8 8 CuO 5274 — CuO 4954.7 4 CuBr
6059.3 10 CuO 5262.3 6 CuCl 4932.0 8 CuF
6045.1 9 CuO 5240 — CuOH 4926.8 6 CuF
5694.3 6 CuF 5237 \ 4901.3 5 CuF
— CuO
5685.7 6 CuF 5228 / 4883.4 4 CuBr
5677.2 5 CuF 5226.1 5 CuI 4881.5 4 CuCl
5550 \ 5220.1 4 Cu 4879.3 8 CuBr
— CuOH
5350 / 5218.2 4 Cu 4781.9 4 CuF
5477.1 4 CuI 5212.2 7 CuI 4515.9 5 CuCl
5402.2 5 CuI 5153.2 4 Cu 4433.8 9 CuCl
5486.5 6 CuI 5141.1 7 CuI 4353.9 10 CuCl
5371.5 5 CuI 5105.5 4 Cu 4341.1 10 CuBr
5344 — CuO 5072.8 10 CuI 4288.6 7 CuBr
5313 — CuO 5061.1 7 CuF 4280.9 9 CuCl
4280.0 — CuH

Page 26 Theory of Colored Flame Production — Douda

Theory of Colored Flame Production — Douda Page 27
 Chromaticity Data

Page 28 Theory of Colored Flame Production — Douda

 Appendix II

1. Contents
Thermodynamic and Physical Properties
Carbon, Hydrogen and Gases
Lithium
Sodium
Potassium
Rubidium
Cesium
Strontium
Barium
Boron
Thallium
Copper

2. Symbols
g = gas state
1 = liquid state
c = crystalline state
K = Kelvin
d = decomposes
ΔHf = heat of formation
ΔF = free energy of formation
D = dissociation energy

3. References cited in following tables.

gf A. G. Gaydon and H. G Wolflard, Flames, Their Structure, Radiation and Temperature,
Chapman and Hall, London, 1960.
g A. G. Gaydon, Dissociation Energies and Spectra of Diatomic Molecules, Chapman and Hall,
London, 1953.
m J. W. Mellor, A Comprehensive Treatise on Inorganic and Theoretical Chemistry, John Wiley,
New York, 16 Volumes, 1937–1961.
r D. Rossini et al., Selected Values of Chemical Thermodynamic Properties, National Bureau of
Standards Circular 500, Feb. 1952.
st D. R. Stull and C. C. Sinke, Thermodynamic Properties of the Elements, American Chemical
Society, Advances in Chemistry Series 18, 1956.

Theory of Colored Flame Production — Douda Page 29

 s T. M. Sugden, Fifth Symposium (International) on Combustion, Reinhold Publishing, New
York, 1955, p 406.
w R. L. Wilkins, Theoretical Evaluation of Chemical Propellants, Prentice-Hall, Englewood
Cliffs, NJ, 1963.
j D. R. Stull et al., JANAF Thermochemical Data, Dow Chemical, Midland, MI, 1960–1963.
Prepared under Advanced Research Projects Agency Program, U. S. Air Force Contract No.
AF33(616)-6149.

Carbon, Hydrogen and Gases

Free Energy j
of Formation Heat of Formation Dissociation Energy
(kcal/mole) (kcal/mole) (kcal/mole)
Species 2000 K 0K 298.15 K 0K 298.15 K
H2O –32.4 –57.1 –57.8 219.3 221.5
H2 0 0 103.2 104.2
OH +2.16 +10.0 +9.3j 100.6 101.6
HF –67.2 –64.2 –65.1j 134.2 134.6
HCl –25.5 –22.0 –22.1 102.2 103.1
HBr –8.6r 86.4g
r
HI +6.7 +6.2r 70.4g
F2 0 0 36.7 36.7
Cl2 0 0 57.1 57.9
Br2 0 0 45.4g
I2 0 0 35.6g
N2 0 0 225.0 225.9
O2 0 0 118.0 119.1
CO -68.4 –27.2 –26.4 256.2 257.3
CO2 –94.7 –94.0 –94.1 381.9 384.5
All gas state.
References: Wilkins except as noted by superscript.

Page 30 Theory of Colored Flame Production — Douda

 Lithium
Free Energy j Heat Dissociation
of Formation of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) (kcal/mole) Point Point
Species State 2000 K 298.15 K 0K K K
Li 1638 j 454 j
–64.2 –l42.6j 276
Li2O c 1700 j
ΔF changes sign from – to + at 3000 K
LiO2 g –37.1. 170 2600gf
+23.0 -27.7j
LiH c 959.6j
ΔF changes sign from – to + at 1200 K
+15.6 -15.1j
LiH l d1245 j
ΔF changes sign from – to + at 1300 K
LiH g +10.7 +32.1j 56 (58g)
j
–37.6 –116.6 263
LiOH c 744 j
–102s
–46.6 –114.1j
LiOH l ~1850 j
ΔF changes sign from – to + at 3100 K
LiOH g –50.0 –57.7j 215
–93.9 –146 202
LiF c 1121 j
–140s 137g
LiF l –98.9 –140j 1966 j
LiF g –98.0 –80.5 j 80.7
–50.1 –97.4 j 115g
LiCl c 880 j
–116s
–55.1 –93.4j
LiCl l 1655 j
ΔF changes sign from – to + at 3700 K
LiCl g –62.8 –43.8j
LiBr c –83.7r 100g 823r
r r
LiBr g –41 1583
LiI c –64.8r 81g 722r
LiI g –16r 1444r
References: Wilkins except as noted by superscript.

Theory of Colored Flame Production — Douda Page 31

 Sodium
Free Energy j Heat Dissociation
of Formation of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) (kcal/mole) Point Point
Species State 2000 K 298.15 K 0K K K
Na 1177 j 371
NaO2 c –61.9 d373m
Na2O2 c –120.6 d 733
Na2O c –1.67 –99.4 >1623m 1190 j
–8.60 –93.2 j
Na2O l
ΔF changes sign from – to + at 2200 K
–13.5 j 47g
NaH c +21.1 at 1500 K d700 j
ΔF changes sign from – to + at 700 K
NaH g +19.4 +29.8
–21.6 –102
NaOH c 593
–83s
–24.9 –100 j
NaOH l ~1450
ΔF changes sign from – to + at 2600 K
NaOH g –38.0 –55.4 j
–72.7 –136 107g 1285 j
NaF c s
–122 1268m
NaF l –77.2 –131j 2100 j
NaF g –73.2 –67j
–41.1 –98.2 97.6g 1081 j
NaCl c s
–96 1077m
–46.8 –93.2j
NaCl l 1790 j
ΔF changes sign from – to + at 3700 K
NaCl g –52.0 –43.5 1738
NaBr c –86 87.5g 1020m
NaBr g –36 1665
NaI c –69 70.6g 935
NaI g –21 1577
References: Rossini except as noted by superscript.

Page 32 Theory of Colored Flame Production — Douda

 Potassium
Free Energy j Heat Dissociation
of Formation of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) (kcal/mole) Point Point
Species State 2000 K 298.15 K 0K K K
K 1039st 336
–86.4 sublimes @
K2O c 1154
600 mm
K2O2 c –118 d1052m 763
K2O3 c –125 d941m 703
KO2 c –134 d933m 653m
–13.8j 42.9g
KH c +23.6 at 1500 K d690j
ΔF changes sign from – to + at 700 K
KH g +21.7 +29.4
–101.8
KOH c 683 j
–86s
KOH l –25.9 –98.7 j 1600
–134.5 115g
KF c s 1775 1129
–126
KCl g –51.6 1680
–104.2 101.4g
KCl c s 1043m
–100
KBr c –93.7 90.6g 1656 1001m
KI c –78.3 76.4g 1597 958
References: Rossini except as noted by superscript.

Theory of Colored Flame Production — Douda Page 33

 Rubidium
Heat Dissociation
of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) Point Point
Species State 298.15 K 0K K K
Rb 974st 312
Rb2O c –78.9
Rb2O2 c –101.7 d1284m 943m
Rb2O3 c –116.7 d1111m 762m
Rb2O4 c –126.2 d1430m 685m
RbH g +33 39g
–98.9
RbOH c 574
–88s
–131.3 123g
RbF c 1681 1048
–124s
–102.9 103g
RbCl c 1654 990
–104s
g
RbBr c –93.0 92 1625 953
RbI c –78.5 77g 1577 913
References: Rossini except as noted by superscript.

Cesium
Heat Dissociation
of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) Point Point
Species State 298.15 K 0K K K
Cs l 958st 302st
Cs2O c –75.9 763
Cs2O2 c –96.2 d1347m 867m
Cs2O3 c –111.2 d1333m 775m
Cs2O4 c –124.2 d1538m 705m
CsH g +29 41g
–97.2
CsOH c 545
–91s
–126.9 127g
CsF c 1524m 955
–128s
–103.5 106g
CsCl c 1573 918
–105s
g
CsBr c –94.3 95 1573 909
CsI c –80.5 78g 1573 894
References: Rossini except as noted by superscript.

Page 34 Theory of Colored Flame Production — Douda

 Strontium
Heat Dissociation
of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) Point Point
Species State 298.15 K 0K K K
Sr 1640st 1043
SrO c –141 106g 3273m 2688
SrO2 c –153
Sr2O c –154
SrH g +52 38g
SrH2 c –42
Sr(OH)2 c –229
SrF g –5 62g
SrF2 c –290 1673
SrCl g +9 58g
SrCl2 c –198 1148
SrBr2 c –171 916
SrI2 c –135 788
SrI 46g
References: Rossini except as noted by superscript.

Barium
Heat Dissociation
of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) Point Point
Species State 298.15 K 0K K K
Ba 1910st 983st
BaO c –133 124g 2273m 2190
BaO2 c –150
Ba2O c –147
BaH g +52 41g
BaH2 c –41
Ba(OH)2 c –226 681
BaF g –9 69g
BaF2 c –287 1673m 1593
BaCl g +24
BaCl c –111 51g
BaCl2 c –205 1235
BaBr2 c –180 1123
BaI2 c –144 1013
References: Rossini except as noted by superscript.

Theory of Colored Flame Production — Douda Page 35

 Boron
Free Energy j Heat Dissociation
of Formation of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) (kcal/mole) Point Point
Species State 2000 K 298.15 K 0K K K
B 3949.9j 2313m
–39.1 +3.74j 188 (175g)
BO g
ΔF changes sign from + to – at 200 K
–119.8 –110.8j 491 Not
(BO)2 g
ΔF changes sign from – to + at 5800 K isolatedm
B2O3 c –188.6 –305 749 723gf
–194.0 –301J
B2O3 l 2520gf
ΔF changes sign from – to + at 4800 K
B2O3 g –177.5 –208 652
BH g +59.7 +06j 68 (69g)
j
BH2 g +41.0 +66.0
BH3 g +33.3 +18 270
j
BF g –87.4 –45.5 196
BF2 g –149 –134j 327
BF3 g –240 –270 458 174r
–1.5 +42.5j 118g
BCl g
ΔF changes sign from + to – at 2000 K
BCl2 g –39.1 –20.7j
–72.6 –97.1j
BCl3 g 285.6r
ΔF changes sign from – to + at 4900 K
BBr g +25r 97g
j
3 –57.9 364.4j
BBr l
–32.5 at 1500 K
–37.2 –49.7j
BBr3 g
ΔF changes sign from – to + at 4200 K
+15.0 +15.0j
between 298 and 6000 K, ΔF is negative only in the 400
BI3 g
to 600 K range. In that range it reaches a
maximum negative of –1.684.
–18.5 –60.3 306
BN c
ΔF changes sign from – to + at 2900 K
BN g +154 92.5 (92g)
References: Wilkins except as noted by superscript.

Page 36 Theory of Colored Flame Production — Douda

 Thallium
Heat Dissociation
of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) Point Point
Species State 298.15 K 0K K K
Tl 1740st 577st
Tl2O c –41.9 773 573
–0 @
Tl2O3 990
1073m
TlH g +48 46g
TlOH c –56.9
Tl(OH)3 c –122
TlF g –33 109g 923 600
TlCl g –16 1079
TlCl c –49 87g 703m
TlCl3 c –83.9
TlBr g –5 1089
g
TlBr c –41 74 732m
TlBr3 c –59
TlI g +7 1098
TlI c –30 60g 713m
References: Rossini except as noted by superscript.

Theory of Colored Flame Production — Douda Page 37

 Copper
Heat Dissociation
of Formation Energy Boiling Melting
(kcal/mole) (kcal/mole) Point Point
Species State 298.15 K 0K K K
Cu 2855 1356
CuO g +35
CuO c –37.1 113g ~2800m 1337m
Cu2O c –39.8 d2073m 1502
CuH g +71 62g
Cu(OH)2 c –107
sublimes
CuF c +44 69g 1181m
1473m
d733 to
CuF2 c –127
CuFm
CuCl g +32
1227m
CuCl c –32 85g 703
to 1327
CuCl2 c –49 d 771m
CuBr g +38
1134m
CuBr c –25 78g 761
to 1227
CuBr2 c –33 d 771m
CuI g +62
1032m
CuI c –16 46g 861
to 1045
Solid not
CuI2 c –1.7
isolated m
References: Rossini except as noted by superscript.

Page 38 Theory of Colored Flame Production — Douda