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Combustion and Flame
Combustion and Flame
Introduction
Previous knowledge of the behavior of pyrotechnic white smoke
compositions of the type zinc oxide-calcium silicide-hexachloroethane
(HCE) has been empirical because of.the technical difficulties of studying
vigorous pyrotechnic reactions by classical methods. The development of
modern techniques such as differential thermal analysis (DTA) [1] has ren-
dered it possible to undertake a study of the complex reactions which
occur in pyrotechnic mixtures.
The range of mixtures of the above type currently employed in British
smoke generators for the production of zinc chloride smokes is as follows:
zinc oxide 47%-29%, calcium silicide 7%-25%, and hexachloroethane
46%. The temperature of burning of this mixture lies in the range from
700oC (low proportion of the fuel, calcium silicide) to 1100oC (high fuel
content), elevation of the temperature resulting in a proportional increase in
the rate of burning of the pyrotechnic mixture.
This paper deals with the pyrolysis of HCE and the identification of the
reactions which occur between the principal constituents of this white
smoke composition, taken in pairs and as a whole. The study is based on
the use of DTA.
The reference material used was calcined alumina of the same weight as
the sample under study. The weights of the sample constituents of each
DTA experiment were taken in the same relative proportions as those
outlined above.
Results
Analytical
Microanalysis of the HCE gave 89.45% (theoretical 89.58%) chlorine, and
gas-liquid chromatography showed only one peak.
Classical chemical and spectroscopic analysis showed the calcium
silicide to contain 32% calcium, 62% silicon, 3% iron, and 2% aluminium,
together with traces of titanium, manganese, magnesium, barium, and
strontium. Thus this material appears from the calcium-silicon phase
diagram [3] to be mainly a mixture of silicon and calcium disilicide (the
approximate atomic ratio being Ca:3Si).
The sample weight taken was 45.8 mg, and the mean heating rate was
4.1oC/min. The changes giving rise to the peaks in Table I can be
summarized as follows:
The peak temperature for each change is given. Accepted values for
transitions A, B, and C are 45', 72', and 187C, respectively. No reference
to phase change D has been found, but analysis of the cell contents after
peak D showed them to be pure HCE.
Peaks E-G were characterized by stopping the DTA run before and
immediately after each peak, quenching the sample cell in cold water, and
analyzing the contents. The initial pyrolysis of HCE to carbon tetrachloride
and tetrachloroethylene has also been postulated by Dainton and Ivin [4].
2. Zinc Oxide (Analar)
When 49.2 mg of zinc oxide was heated from room temperature to 900 oC
at a mean heating rate of 4.0oC/min, no peaks were observed in the
differential thermogram.
3. Calcium Silicide
At a mean heating rate of 4.3oC/min from 20oC to 900oC, 49.6 mg of
calcium silicide appeared to be thermally stable since no DTA peaks were
observed.
It was found that reaction proceeded in several stages since two sets of
peaks were observed. As the calcium silicide content of the mixture
increased, the first set of exothermic peaks was poorly resolved into a
triplet (Table 2) at 372'-375'C. These peak temperatures were little affected
by changing the HCE/calcium silicide ratio. The peak a rea, however,
showed a definite reduction as the calcium silicide content increased. This
is to be expected from the work of Sewell and Honeyborne [5], who
showed that peak area is directly proportional to the heat of reaction per
unit mass of reacting material multiplied by the mass fi-action of this
material in the sample.
Support for the above scheme was furnished by heating the mixture to
900'C when the DTA record exhibited a sharp endotherm at 772oC, in
agreement with the accepted value for the fusion of calcium chloride.
Furthermore, DTA of calcium silicide mixed with each of the above reaction
intermediates resulted in the carbon tetrachloride mixture giving three
exotherms (at 345o, 349o, and 402oC), tetrachloroethylene two (at 396o
and 516oC, and hexachlorobenzene one (at 463oC.
The silicon moiety of the calcium silicide was thought to rea ct little if at all
with HCE (or its decomposition products) since DTA of this element and
chlorinated hydrocarbons resulted in a small broad exotherm (slow
reaction at about 380oC.)
5. HCE + Zinc Oxide (Analar)
The reaction intermediates were identified after each peak, those after
peak A being mainly HCE, tetrachloroethylene, and carbon dioxide,
together with small amounts of carbon tetrachloride and phosgene;
substantial amounts of zinc oxide also remained after this first reaction
sequence. It seems probable therefore that some stable zinc oxychloride
of empirical formula 2ZnO - ZnG2 is formed. The singlet nature of peak A
is probably due to the comparatively low temperature of the reactions of
carbon tetrachloride (224'Q and phosgene (277'Q with zinc oxide as
compared with the temperature of the reaction sequence shown above.
The reaction(s) responsible for exotherm B cannot be ascribed with any
certainty from the available results. There exist three possibilities, these
being (1) the zinc oxychloride reacts with tetrachloroethylene thus:
Finally, it should be noted that the reaction of HCE with zinc oxide is
much less exothermic than with calcium silicide.
Thus, on stopping the DTA run after exotherm B, the volatile produc ts
were found to be mainly tetrachloroethylene, carbon dioxide, and some
HCE. It may be noted that in these ternary mixtures exotherm B occurs at
50'-80'C below the lowest exothermic peak temperatures found in any of
the binary mixtures. This is probably due to the extremely rapid rate of
reaction of zinc oxide with carbon tetrachloride (see Section 5) as the latter
is initially produced at about 300'C as shown above; the singlet nature of
peak B is similarly explained. As the calcium silicide content of the mixture
decreases, peak B is reduced in size, since less carbon tetrachloride is
available for reaction with the zinc oxide.
Practical Considerations
Conclusions
The ease and the extent of smoke formation are directly dependent on
both the fuel (calcium silicide) and the smoke producer (zinc oxide) content
of the pyrotechnic mixture.