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Combustion and Flame
Combustion and Flame
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:
C2Cl6 (rhombic) ? C2Cl6 (triclinic)
A (51oC)
C2Cl6 (triclinic)
? C2Cl6 (cubic)
B (75oC)
C2Cl6 (cubic)
? C2Cl6 (liquid)
C (188oC)
C2Cl6 (liquid)
? C2Cl1 (gas)
D (278oC)
2C2Cl6
? 2CCI, + C2Cl4
2CCl4
? C2Cl4 + 2Cl2
E (728oC)
3C2Cl4
? C6Cl6 + 3Cl2
C6Cl6
& nbsp; ? 6C + 3CI2
F (830oC)
2C+02
? 2CO
G (874OC)
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.
4. HCE + Calcium Silicide
Initially 46 mg of HCE and 7-25 mg of calcium silicide were heated at a
nominal rate of 4oC/min (Table 2). The four HCE transitions were observed
at the expected temperatures, and the exothermic peaks thus
corresponded to reaction of the solid inorganic with the gaseous organic
component.
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.
Following the multiplet exotherm was a single exothermic peak. This
increased in size and appeared at successively lower temperatures as the
proportion of calcium silicide increased.
Optimum resolution of the multiplet exotherm. was achieved when a 20-mg
HCE- 12 mg calcium silicide sample was used (Fig. 1). The exothermic
peaks were characterized by analysis of the products of reaction after each
peak, thus:
CaSi3 + 3C2Cl6 ?
2CaSi3 + 2CCl4 ?
3CaSi3 + 3C2Cl4 ?
3CaSi3 + C6Cl6 ?
A (381oC)
;
B (387-C)
C (398-C)
D (472-C)
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 al
l
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)
When 46 mg of HCE was heated with 47-mg to 29-mg quantities of zinc
oxide at a nominal heating rate of 4'C/min, the usual HCE transitions were
observed. Hence the reactions of these two compounds were of the
gas-solid type.
It was found that the reaction peaks were not significantly affected (with
regard to peak area or temperature) by variation of the zinc oxide content
of the mixture. Figure 2 is therefore representative of all the mixtures used
(see Table 3). The DTA peaks in Fig. 2 are thought to be due to the
following reactions:
2C2Cl6 ? 2CCl4 + C2Cl4
6ZnO + 2CC14 ? 2(2ZnO.ZnCl2) + 2COCl2
A (348oC)
6ZnO + 2COC12 ? 2(2ZnO.ZnCl2) + 2CO2< BR>Not fully elucidated
B (443oC)
Pyrolysis of excess chlorinated hydrocarbons
(see Section 1)
C (686oC
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:
2ZnO - ZnCl2 + C2Cl2 --+ 3ZnCl2 + 2CO
(DTA of zinc oxide + tetrachloroethylene gives the above products at a
peak temperature of 533oC, or (2) the oxychloride reacts with excess HCE
by a scheme similar to that for peak A (Fig. 2), or (3) the first and second
mechanisms could proceed concurrently. The second of these possibilities
seems the least likely at the present time since after peak B the amount of tetr
achloroethylene in the
sample cell was low and a substantial amount of carbon monoxide was
found.
Finally, it should be noted that the reaction of HCE with zinc oxide is
much less exothermic than with calcium silicide.
6. Zinc Oxide + Calcium Silicide
Mixtures of these two substances heated to 90oC at a nominal rate of
4oC/min were found to be chemically inert.
7. Zinc Oxide + Calcium Chloride
This binary system was studied since DTA of a complete pyrotechnic white
smoke composition (see Section 8) did not show a calcium chloride fusion
endotherm. as expected. The two components were taken in
equirnolecular quantities (total weight 50 mg) and heated at a nominal
4oC/min in a sealed quartz cell. The only DTA peak observed was the
calcium chloride melting endotherm at 771oC.
8. HCE + Zinc Oxide + Calcium Silicide
These components were examined in various ratios corresponding to the
smoke composition in current use, sample weights being 100 mg total. At a
nominal heating rate of 4oC/min the usual HCE transitions were observed
(peak A, Fig. 3, being the vaporization endotherm) be fore reaction of this
compound with the inorganic solids.
The following reaction scheme is believed to account for exothermic
peaks B-E in Fig. 3 and Table 4:
Combustion of a Pyrotechnic White Smoke Composition
CaSi3 + 3C2Cl6 CaCl2 + 2CC14 + 2C2Cl4 + 3Si
6ZnO + 2CCl4 ? 2(2ZnO-ZnCl2) + 2COCl2
B
6ZnO + 2COCl2 ? 2(2ZnO-ZnCl2) + 2CO2
3CaSi3 + 3C2Cl4 ? 3CaCl2 + C6Cl6 + 9Si
C
2ZnO-ZnCl2 + C2Cl4 ? 3ZnCl2 + 2CO
3CaSi3 + C6Cl6 ? 3CaCl2 + 6C + 9Si
D
E
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.
After peak C the organic products were found to be mainly
hexachlorobenzene together with some tetrachloroethylene, the latter
probably being produced from any excess HCE remaining after reaction
sequence B. Exothermic peak C is seen to decrease rapidly and finally
disappear on reducing the calcium sili cide content of the ternary mixture.
Also, peak E decreases similarly since reaction C is the source of the
hexachlorobenzene reactant for reaction E.
The exothermic reaction giving rise to peak D produced substantial
quantities of carbon monoxide, indicating the reaction of zinc oxychloride .
(or oxide) with tetrachloroethylene. Peak D becomes more pronounced as
the calcium silicide content of the mixture decreases, since more
tetrachloroethylene becomes available for reaction by virtue of reaction C
being diminished.