Page 8 PGI Bulletin No.

46, March, 1985

THE FEW, THE PROUD, THE SULFATES
By Donald J Haarmann

Having lost the original file! This was scanned in. And you know what
that means!!

Most sulfates are not water soluble, are geologically stable and can be
easily and cheaply obtained by mining, rather than having to be produced
through complicated and expensive chemical processing. Therefore
sulfates pass the first test for possible inclusion in any pyro formula; they
are inexpensive. Indeed native sulfates such as barite (BaSO4) and
celestite (SrSO4) are the starting materials for other barium and strontium
compounds used in fireworks.

Sulfates certainly appear attractive because their oxygen content compares

favorably with that of metal chlorates, perchlorates and nitrates, as Table 1
illustrates. Also a comparison of the heat evolved from reaction of
aluminum and various oxidizing agents again shows that sulfates compare
favorably with more familiar pyrotechnic oxidizers. (See Table 2.)

Table 1
Percent oxygen contained (percent by weight) for various pyrotechnic
oxidizers and sulfates, for the anhydrous compound.
Nitrate Chlorate Perchlorate Sulfate
Ammonium 0.60 0.47 0.54 0.48
Barium 0.37 0.32 0.38 0.27
Calcium 0.58 0.46 0.41 0.47
Copper 0.51 0.42 0.49 0.40
Gadolinium 0.42 0.35 0.42 0.32
Lithium 0.69 0.53 0.60 0.58
Magnesium 0.65 0.50 0.57 0.53
Potassium 0.47 0.39 0.46 0.37
Sodium 0.56 0.45 0.52 0.45
Strontium 0.45 0.38 0.45 0.47

Table 2
Heat produced (cal/g) from a mixture of an oxidizer or sulfate with
aluminum. Values from AMCP 706 185(1967) and/or Vasilev (1973) (*).

Sodium perchlorate 2,600 Lead nitrate 1,500

Sodium chlorate 2,500 Barium nitrate 1,400
Potassium per chlorate 2,400 Copper sulfate 1,400/1,560*
Potassium chlorate 2,200 Calcium sulfate 1,300/1,470*
Sodium nitrate 1,800 Sodium sulfate 1,200/1,360*
Potassium nitrate 1,800 Potassium sulfate 1,200/1,180*
Lithium sulfate 1,620* Barium sulfate 900/910*
Magnesium sulfate 1,610* Lead sulfate 800
Ammonium nitrate 1,600

However, low cost is not the only criteria for selecting oxidizers for use in
fireworks compositions. A quick check of Table 1 reveals several
oxidizers with high oxygen content, for instance, calcium, sodium, and
ammonium nitrates, sodium chlorate, and magnesium perchlorate.
However, of these only sodium nitrate has found use, albeit limited
primarily to military pyrotechnics. All of these compounds are
hygroscopic and therefore unusable in the real world. In fact, magnesium
perchlorate is used as a drying agent under the trade name of
"Anhydrone".
There can be no doubt that the largest problem concerning the use of sul
fates as oxidizing agents is their waters of hydration, for example:

Na2504 10H2O and Cu(SO4) 5H2O. Although the ten extra oxygen atoms
in sodium sulfate raise its total oxygen content from 45% to 70%, this
extra oxygen contained in the waters of hydration is not available for
productive work. In truth it only gets in the way, since a large amount of
heat is required to first remove the water of hydration from a composition's outer
surface before the ignition temperature can be reached. Then once the
reaction becomes self sustaining, even more heat, produced by a burning star for in
stance, will be removed from the reaction in the form of vaporized water.
(It should be noted that the latent heat of vaporization for water is 540 cal
ories per gram of water at 100� C. This value represents heat that must be
supplied by the pyrotechnic reaction to change water at 100� C into steam
at 100� C.) There is also the possibility, in magnesium containing
compounds, of the water vapor reacting with the magnesium forming
hydrogen and magnesium oxide, effectively removing a large amount of
fuel, with little gain in heat. In the case of sodium sulfate decahydrate,
where 56% of each molecule is water, 31,920 calories of heat would have
to be supplied simply to remove all the water of hydration in the form of
steam from each 100 grams of sulfate. For example, in a composition
using potassium perchlorate as the oxidizer and aluminum as the fuel, 13.3
grams of aluminum and potassium perchlorate would be needed just to
remove the water from each 100 grams of sodium sulfate decahydrate,
before any useful work (heat and/or light) would be produced!

As a further complication, the temperature at which waters of hydration

are liberated varies from sulfate to sulfate, e.g., sodium sulfate
decahydrate loses all its water at 100� C while manganese sulfate
monohydrate does not lose all its water until the temperature reaches 400
450� C! And to really complicate things, manganese(ll)sulfate can exist as
either mono, tri-, tetra , penta, hexa, or heptahydrate! Although the
tetrahydrate is the most common form.

However, US Patent 2,885,277 claims to make use of the waters of

hydration in magnesium sulfate heptahydrate, MgSO4 7H2O (Epsom
salts), to produce hydrogen gas when the sulfate is reacted with
magnesium. It is further claimed that this combination will function as
either a torch or a salute. It would be well to note that Ellern (1968, p.
272) expresses doubt concerning the safety and utility of such mixtures.

The use of sulfates as oxidizers suffers from yet another problem. As Dr.
Conkling (in press) has pointed out "In pyrotechnics, the solid liquid
transition appears to be of considerable importance in initiating a self
propagating reaction. The oxidizing agent is frequently the key component
in such mix tures, and a ranking of common oxidizers by increasing
melting point bears a striking resemblance to the reactivity sequence for
these materials." Unfortunately the melting point of most sulfates is much
higher than either chlorates, perchlorates or nitrates. Only four sulfates
(manganese, copper, zirconium and iron) have melting points below that
of barium nitrate, and these four are well hydrated (tetra or penta .)
Melting points are summarized in Table 3.

Table 3
Melting point for various anhydrous oxidizers and sulfates. Values are
from the CRC Handbook. d decomposes, sd slight decomposition.

Copper perchlorate 82 Silver perchlorate 486

 Iron perchlorate >1OOd Thorium nitrate 500
Strontium chlorate 120d Thallium perchlorate 501
Lithium chlorate 128 Barium perchlorate 505
Scandium nitrate 150 Strontium nitrate 570
Manganese(111) sulfate 160d Barium nitrate 592d
Americium nitrate 170 Zinc sulfate 600
Copper sulfate 200sd 650d Thallium(l) sulfate 632
Silver chlorate 230 Silver sulfate 652
Lead chlorate 230 Manganese(ll) sulfate 700
Lithium perchlorate 236 Lithium sulfate 845
Sodium chlorate 248 Nickel sulfate 848
Magnesium perchlorate 251d Sodium sulfate 884
Lithium nitrate 264 Ytterbium(111) sulfate
900
Calcium perchlorate 270 Yttrium sulfate 1000
Sodium nitrate 307 Cesium sulfate 1010d
Rubidium nitrate 310 Rubidium sulfate 1060d
Potassium nitrate 334d Potassium sulfate 1069
Calcium chlorate 340 Samarium sulfate (basic)
1100
Potassium chlorate 356 Magnesium sulfate 1124d
Potassium perchlorate 400d Lanthanum sulfate 1150
Zirconium sulfate 410d Lead sulfate 1170d
Cesium nitrate 414 Calcium sulfate 1450
Barium chlorate 414 Barium sulfate 1480
Iron sulfate 480d Strontium sulfate 1605d
Sodium perchlorate 482

It is evident that getting compositions based on sulfates as oxidizers to ig

nite while not impossible ... is not going to be easy. There can be no doubt
that it is going to take an extremely hot ignition source!

Copper sulfate with its low melting point looks like a prime candidate but
again, the water of hydration is a problem. Exposed to moist air, CuSO4
becomes CuSO4 .H2O, and when wetted, CuSO4.5H2O. Also, because
copper sulfate is water soluble, it is seldom found in native form
(chalcanthite). Therefore it is manufactured from copper metal and
sulfuric acid, and as a result fails the first test, it is not cheap. It is also
not
safe with chlorates.

Although certainly attracting because of their low cost oxygen content,

sulfates have for the most part, not been employed as oxidizing agents.
How ever, them have found their niche in strobe formulas.

Vander Horck (1974) reported on several formulas using calcium and

copper sulfates demonstrated to him by Bob Winokur who later (Winokur,
1974) made additional comments about them. Further Dr. Shimizu (1981)
presents several strobe ("twinkler") formulas using sulfates, i.e., strontium,
barium, sodium and calcium. Advantage is taken of the great difficulty of
igniting and then sustaining ignition in sulfate based compositions.
Therefore flashes of light are produced each time the sulfate reaches
its melting point or decomposition temperature, burning commences
and shortly thereafter extinguishes only to repeat, producing the strobe light
effect.

Sulfates have long been used in color flame compositions more for their
metal than oxygen content. However, for the most part, the color produced
by sulfate based compositions not containing metal fuels such as
aluminum or magnesium, will be found to be less than satisfactory, since
only metal fuels are capable of producing the high temperatures necessary
to melt or decom
pose most sulfates. The use of various sulfates is detailed below:

Copper sulfate: In older literature, e.g. Kentish (1878) compositions for

blue flames can be found using copper sulfate and potassium chlorate,
where the copper ion is used to produce the blue color. THIS
COMBINATION IS DAN
GEROUS. Safer and more effective blue formulations are available.

Barium sulfate: Troy Fish (1981) recommends the use of barium sulfate in
parlon bound green stars. He notes that as a result of barium sulfate's
extreme insolubility (0.000413 grams per 100 ml of boiling water!), it is
one of the few nontoxic barium compounds. I have been able to locate
only seven formulas using barium sulfate, and all seven use either
magnesium, aluminum or magnalium.

Calcium sulfate: Despite the many obstacles noted above, calcium sulfate
hemihydrate (plaster of Paris) [CaSO4 ~H2O] has been used as an
oxidizer in fireworks and pyrotechnics: In combination with sodium and
barium nitrate in white light compositions (Ellern, 1968, formulas 36, 37
and 38), as an incendiary when combined with aluminum (US Patent
2,424,937, Vol. 3 of the "Black Book", 1982), or aluminum and
magnesium sulfate (US Patent 4,381,207), and when compounded with
aluminum, Teflon, and sulfur (US Patent 4,349,396) as a metal
cutting torch.

Calcium sulfate combined with either aluminum or magnesium has been

suggested as a "flash report" mixture! (Sanford, 1974)

This sulfate is found in pink tableau fire or star compositions using

potassium perchlorate as the oxidizing agent. Weingart (1947) has the
only modern for
mula I have been able to locate that uses calcium sulfate without either
aluminum, magnesium or magnalium.

Potassium sulfate: The Technico Chemical Receipt Book 1896 long ago
recommended the use of potassium sulfate in blue compositions. There is
only one modern formula using potassium sulfate, Dr. Shimizu's white
"twinkler" using magnalium as the metal fuel.

Strontium sulfate: This sulfate had long ago been used in the production of
red or purple flames. However, there are no formulas using strontium
sulfate in Lancaster, Ellern or Weingart. There are however, three
"twinkler" for mulas in Shimizu using strontium sulfate. All three contain
magnalium.

Sodium sulfate: I have been able to locate only four formulas using
sodium sulfate, all by Dr. Shimizu, who uses sodium sulfate in
combination with magnalium for yellow strobe stars.

Manganese sulfate: Perhaps the most interesting use of sulfate is the

addition of manganese sulfate (MnSO4 H2O) to aluminum sodium nitrate
flare compositions. Farnell et al.(1972) discovered that this compound
alters "the decomposition of sodium nitrate to form oxides of nitrogen
rather than its normal decomposition products of nitrogen and oxygen."
This change results in a 55% decrease in burning rate, a 155% increase in
luminous output, and a 466% increase in luminous efficiency!
Although not a mainstays of the fireworks trade, sulfates have found
employment along with the proverbial kitchen sink, used frying pans, oil
of spike and philosopher's wool!!!

Literature cited

AMCP 706 185, 1967, Engineering Design Handbook, Military

Pyrotechnics Series Part 1; Theory and Application. NTIS AD 817071.

Black Book, 1982, Improvised Munitions Black Book, Vol. 3. Desert

Publications.

Conkling, J., (in press), The Chemistry of Pyrotechnics and Explosives:

Basic Principles and Theory. Marcel Dekker, New York.

CRC Handbook of Chemistry and Physics, 1981, 62nd edition.

Ellern, H., 1968, Military and Civilian Pyrotechnics. Chemical Publishing

Inc., NY.

Fish, T., 1981, Green and other colored flame metal fuel compositions
using parlor. Pyrotechnica Vll, pp. 25-37.

Farnell, Westerdahl and Taylor, 1972, The Influence of Transition Metal

Compounds on the Aluminum Sodium Nitrate Reaction. Third
International Pyrotechnics Seminar.

Kentish, T., 1887, The Pyrotechnists Treasury, The Complete Art of Fire
Making. Chatto and Windus, London.

Sanford, R., 1974, Plaster of Paris flash powders, American Pyrotechnist

Fireworks News, p. 527.

The Technico Chemical Receipt Book 1896. As reprinted in: Kurt Saxon's
1972 The Poor Man's James Bond, Atlan Formularies, Eureka, CA, p. 65.

Merck Index, 1983, The Merck Index: An Encyclopedia of Chemicals,

Drugs, and Biologicals. Merck and Co., 10th edition.

Shimizu, T., 1981, Fireworks: The Art, Science, and Technique. Maruzen
Publishing Co.

US Patent 2,424,937, July 1947, Incendiary Composition.

US Patent 2,885,277, May 1959, Hydrogen Gas Generating Propellant

Compositions.

US Patent 4,349,396, September 1982, Metal Cutting Pyrotechnic

Composition.

US Patent 4,381,207, April 1983, Pyrotechnic Composition.

Valsilev, A.A., et al., 1973, Combustion of mixtures of metal sulfates with

magnesium or aluminum. Translated from Russian. NTIS AD 785988, 5
pp.

Vander Horck, M.P., 1974, Unconventional star compositions

demonstrated. American Pyrotechnist Fireworks News, 7(4), issue no.
76, p. 506.

Weingart, G. W., 1947, Pyrotechnics. Chemical Publishing Co., NY,

pages 61 and 134.

Winokur, R., 1974, More on unconventional stars. American Pyrotechnist

Fireworks News, 7(5), issue no. 77, p. 516.