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Royal Society is collaborating with JSTOR to digitize, preserve and extend access to Proceedings of the
Royal Society of London. Series A, Mathematical and Physical Sciences
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The thermal oxidation of methylene chloride
A study of the kinetics of the slow oxidation of methylene chloride has been made using
a static system and the results of this are compared with those of flow-system experiments in
which the composition of the reacting system was determined in considerable detail by gas-
chromatographic analysis. The reaction shows all the symptoms of a degenerately branched
chain process and is similar to the corresponding thermal decomposition reaction in many
respects. Several of the chlorinated hydrocarbon minor products are identical with those
found in the thermal decomposition and this, together with kinetic evidence, suggests that the
primary chain is the same in both reactions, oxygen intervening only in the conversion of the
intermediate, dichlorethylene, to the end products HCI and carbon monoxide, and in the
branching step, through which it modifies the overall rate.
As in the thermal decompositon several of the organic minor products are susceptible to
attack by chlorine atoms participating in the main chain and this prevents an accurate
evaluation of the chain length by measurement of the rate of formation of termination
products. The average chain length, however, appears to be of the order of ten. Methylene
chloride+ oxygen mixtures show a single explosion limit above about 600 00, which obeys
the Semenov equation log10 p =A/T+B, A being a constant for the system and B depending
on the geometry of the vessel.
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198 M. R. Hoare, R. G. W. Norrish and G. Whittingham
Section 2 describes recent work by Norrish & Hoare in which the changing
composition of the reacting system has been studied in considerable detail by
a combination of flow system and gas-chromatographic analysis. The results of
both investigations, which are closely connected with the study of the thermal
decompositioil of methylene chloride described in the preceding paper (Hoare,
Norrish & Whittingham I959), are presented here and discussed together.
Experimental
The apparatus described was of the conventional type for studying pressure
changes during reaction and was practically identical with that described in the
previous paper on the thermal decomposition of methylene chloride. The furnace
used was fitted with a window which made possible the observation of flame
phenomena and the reaction vessel was connected to a vacuum system including
traps, a Toepler pump and a Bone and Wheeler apparatus.
Oxygen was prepared by electrolysis and purified by passage over plantinized
asbestos followed by distillation from liquid air in which the first fraction was
discarded. Nitrogen was taken from a cylinder and purified by passage over heated
copper at 400 ?C and potassium hydroxide, then through a spiral cooled in liquid
air. Methylene chloride was obtained by redistillation of the pure grade followed
by drying over calcium chloride.
RESULTS
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The thermal oxidation of methylene chloride 199
minutes (table 2). Table 3 shows the variation of maximum rate and percentage of
fast reaction with vessel diameter. In very narrow vessels the reaction was
virtually completely inhibited. In the presence of nitrogen the reaction is
accelerated, the maximum rate being approximately proportional to the pressure
mmT CHa202+ rn ? 2
60 - C ; TQ
240
20
time (min)
FIGURE 1. The oxidation of methylene chloride T -00 ?C; vessel diameter, 34 mm.
temperature
(OC) (min-')
527 0*09
552 0.20
565 0.25
605 1*41
of inert gas in a vessel of internal diameter 21 mm (table 4) but rather less than
proportional with a diameter of 34 mm. Addition of excess of the products HCI
and C02 to the mixture produced an accelerating effect identical with that
of nitrogen. The presence of added CO had only the normal inert gas effect at
low temperatures; at higher temperatures the results were confused by its own
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200 M. R. Hoare, R. G. W. Norrish and G. Whittingham
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The thermal oxidation of methylene chloride 201
200 ;0 ck
\0%
100 - 40-
0 ~~~~~~~~~~0
700 800 0 10 20
temperature ("C) induction period (see)
FIGuRE 2. The explosion limits of FIGuRE 3. The dependence of 'induction
methylene chloride+oxygen mix- period' on pressure in explosion --)
tures vessel diameter= 25 mm. and slow reaction (--). 1: 3-CH2C12 + 02
mixture; vessel diameter= 34 mm.
Experimental
Except for some minor changes in the arrangements for trapping the products
the flow system used in this work was identical with that described in the previous
paper on the thermal decomposition reaction. Methylene chloride was purified as
before; oxygen taken from a cylinder was dried before use by passage throug
phosphorus pentoxide and a trap containing glass beads at -78 'C.
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202 M. R. Hoare, R. G. W. Norrish and G. Whittingham
Experimental procedure
From the results obtained with the static apparatus and from preliminary
experiments with the flow system, it was clear that under flow conditions at
1 atm. total pressure, the reaction could only be studied at a temperature suffi-
ciently low to avoid appreciable pyrolysis if a mixture rich in methylene chloride
were used. The experiments were therefore restricted to the case of a 1: 1 CH2C12 + 02
mixture reacting at 579 0C which is about 30 ?C below the explosion limit at 1 atm.
Two different vessels having surface/volume ratios of 1P76 and 463 cm-1, respec-
tively, were used. The latter was bent into a loop in order to be accommodated in
the furnace. After allowing a considerable time for the equilibrium of the reaction,
the products were collected in two different ways, as follows:
(i) The effluent gases were passed through a trap packed with glass wool at
- 78 ?C for at least sufficient time for the dead space of the trap to be swept out.
After a known time the trap was isolated and cooled in liquid oxygen to leave
a sample of the permanent gas products in the dead space, which could be removed
by Toepler pump for analysis. The remaining condensable products were then
distilled into weighed sample tubes, HC1 and CO2 were distilled off at -78 00 and
the tubes were sealed under vacuum and weighed.
(ii) A second sample was then collected during a known time in a trap cooled in
liquid oxygen, a proportion of nitrogen being mixed with the gas stream immediately
after the reaction zone in order to prevent the condensation of liquid oxygen. The
total condensate was then distilled into a system of known volume where its
pressure could be measured and samples were dispensed for analysis as described
below.
Analytical procedure
Carbon monoxide. In the absence of other possible permanent gases in the pro-
ducts, carbon monoxide was determined by measurement of the pressure drop on
removing oxygen from a sample with a phosphorus tube. A correction was made
for the amount of CO2 formed in calculating the value of' mol. CO per mol. CH2C12 in'.
Hydrogen chloride. HC1 was determined by extracting a known sample of
products with water and titrating the solution against standard caustic soda.
Carbon dioxide. C02 was determined by gas chromatography of a sample of
condensable products, using a 2 m Tricresyl phosphate column at room temperature,
with hydrogen carrier-gas.
Liquid products. The liquid products after being separated from HC1 and CO2 by
distillation at -96 0C were analyzed by gas chromatography using two partition
columns of different stationary phases (Tricresyl phosphate and Apiezon-L) and
at temperatures of 78, 96 and 145 'C. The following compounds were identified as
minor products under at least three conditions of temperature and stationary
phase: CHC12CHC12, CHCl: CC12, CHC013, CC14, cis- and trans-C2H2C12, CH2: CC12 an
C2Cl4. All these except the first three were present only in very minute amounts.
The apparatus enabled quantities of about 0.5 to 5.0JLmol. of the above to be
detected, depending on their boiling point, which corresponded to solutions of
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The thermal oxidation of methylene chloride 203
Egriwe's (I937) method. One part per million of formaldehyde in water could be
detected in this way.
CH2CI2-
(lowsensitivity)
C2HC13
5 10 15 20 25 30 min
030018 1-66 7 00 210
weight % in CH2C12
RESULTS
The product curves for the reaction of a 1: 1 CH2C12 + 02 mixture at 579 0C are
shown in figure 5. Here the upper curves represent the formation of the major
products HC1, CO, C02 in terms of 'mol. product per mol. CH2C12 in', the lower
curves show the formation of the various minor products similarly but on a scale
some two hundred times larger. The formation of formaldehyde and water is shown
on a more convenient scale in figure 6. The true contact time, in terms of which
these results are plotted, was calculated by the method described in the preceding
paper.
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204 M. R. Hoare, R. G. W. Norrish and G. Whittinglham
HCI
* . 15_
10~~~~~~~~~
1.0-~ ~ ~ ~ ~ ~ 2
0 20 40 60
10_
A C2HCI3
2 - C7'2CI4 A
ACHCI3
00 4 - .-. C2C14
O 3a
2- HCHO2 cis-C2ZH2C12
0 20 " 40 60
time (see)
FIGURE 5. The oxidation of CH2C12 at 579 'C. S/V= 1 76; Pelf2C12 P02= 380 mm
4-
0 20 40 60
10_
10 4 0
0 20 40 60
time (see)
FIGURE 6. The oxidation of CH2C12 at 579 'C: the formation of H20 and HCHO.
S/V= 1F76; PH2012 = P02 = 380 mm. - --, overall reaction.
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The thermal oxidation of methylene chloride 205
DiSCUSSION
The results of the static experiments described in ? 1 leave little doubt that the
oxidation of methylene chloride, like its thermal decomposition, is a degenerately
branched chain process. The existence of an incubation period, the acceleration in
the presence of inert gas and sensitizers and particularly the complete inhibition at
low vessel diameters again offer the strongest possible evidence for this. Accepting
this diagnosis, the results of minor product analysis will be used as before to decide
the finer points of the mechanism.
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206 M. R. Hoare, R. G. W. Norrish and G. Whittingham
2-
HCI
S/V=1.76 /
S/V=4 63
0 20 40 60 80
15
, CHC
A C2HC13
o 10
0 X~~~~~HCH3
time (sec)
the minimum rate of pyrolysis relative to oxidation compatible with fast reaction,
but the formation of free carbon could, nevertheless, be observed during the reac-
tion. The similarity of oxidation and decomposition is also apparent in the maxi-
mlum rate- equations, which are of the second order in methylene chloride pressure
in each case, and in the pattern of minor product formation. In the oxidation
symntetrachlorethaue and trichlorethylene are again the principal organic minor
products, though the balance of hydrogen seems to appear this time as water
instead of methyl chloride. This may, however, be an indirect result of the presence
of oxygen.
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The taherml oxidation of methylene chloride 207
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208 M. R. Hoare, R. G. W. Norrish and G. Whittinghamr
Once again all the stable compounds shown enclosed can be detected in the
system, and these comprise the complete list of detectable minor products, except
for the minute traces of formaldehyde, 1: l-dichlorethylene and carbon tetra-
chloride. The question of formaldehyde formation will be examined later.
Solution of the stationary-state equations for the above scheme with the
assumption that (7) is the only significant termination step and that this is
infrequent compared with reaction (2), leads to the expression
where the k's are the rate constants corresponding to the various elementary
reactions above, P is the total pressure of the system, d is the vessel diameter and d-
is a factor representing the specific activity of the surface. The way in which these
factors contribute to the termination step has been explained in the preceding paper.
This expression agrees well with experiment as regards the dependence of maxi-
mum rate on reactant concentration, subject to the assumption that the 'steady-
state concentrations' appearing in the equation are equal to or proportional to the
initial values. The proportionality of maximum rate to total pressure is also borne
out experimentally, but its dependence on the vessel diameter is found to be
nearer to a 1-5 power law than the first power law required by the above expression.
* The full details of the chain reactions of decomposition and oxidation of dichlorethylene
have not yet been fully worked out. Reactions (4) and (5) possibly, summarize a sequence
of reactions.
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The thermal oxidation of methylene chlortde 209
Reactions (1), (2) and (3) are exactly as proposed for the thermal decomposition
reaction. Since the rate constant for reaction (4) does not appear in the final
expression, this can be replaced by any other process giving the same net result.
Alternative possibilities are that the C2HC12g radical is converted to dichloracetylen
or carbon, with the subsequent oxidation of either of these. Reaction (5), must
clearly involve oxygen as was explained earlier. The most striking evidence for the
participation of oxygen in the branching step is provided by a comparison of the
temperature dependence of the branching factors, qS, in the decomposition and
oxidation reactions. Values of 0 were obtained for a single initial pressure of
reactants at different temperatures by application of the equation ln Ap = 0bt to
the initial portion of the pressure-time curves (table 2 in the preceding paper and
table 2 in this paper). For the decomposition the variation of 0 with temperature
could be expressed by 0 = 0 exp (- 46000)/RT, whereas in the oxidation the
expression - = 00 exp (-26 000/IRT) was obtained. The lower value for the 'energy
of branching' in the case of the oxidation seems to be strong evidence that oxygen
is directly involved in the branching step.
Kinetically, equation (5) could be any reaction of the intermediate with oxygen
which leads to an increase in chain centres. The possibilities are limited, however,
and the version given has the advantage of accounting for the presence of water in
the products. However, since water is not formed in constant ratio to HCO, this
may not be the only reaction leading to its formation.
The ratio of chloroform to tetrachlorethane and trichlorethylene is small in the
early stages of the reaction but it is significantly larger than in the thermal
decomposition. This is more likely to be due to the lower temperature used than to
the presence of oxygen. Free chlorine is again only detectable in minute amount,
so that the neglect of equations (8) and (9) in the steady state calculation is
probably justified.
The direct evidence that dichlorethylene is the degenerate branching agent is
somewhat stronger here than in the thermal decomposition study. Not only does
the addition of a trace of this substance to the system remove the incubation
period without changing the maximum rate, but in the minor product analysis
(figure 5) the concentration of ci8-dichlorethylene in the reacting system may be
seen to rise to a distinct maximum at the point of maximum overall velocity, as
would be required. Very little of the trans-isomer could be detected, which is to be
expected since isomerization is known to occur in favour of the cis configuration
at high temperatures. the same considerations apply to the growth of recombina-
tion products in the system as were discussed in the case of the thermal decom-
position. The fall in their concentration relative to HCI as the reaction proceeds
may be attributed to attack by chlorine atoms as before. The sharp fall in the
concentration of C2H2C14 in figure 5 just before the point of maximum overall
velocity, however, requires an additional explanation. It seems impossible that
this should be due to a kinetic effect and it is most probably the result of the libera-
tion of heat during the fast phase of the reaction. The rate of liberation of heat
during the reaction of an equimolar mixture at one atmosphere total pressure in
the flow system would be considerable and would be 'localized' in a narrow band
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210 M. R. Hoare, R. G. W. Norrish and G. Whittingham
of the reactor. This conclusion is supported by the fact that in the experiments at
high surface/volume ratio where less temperature rise would be expected, there is
no such sharp fall in C2H2C14 concentration (figure 7). The fact that in figure 5 the
CjH2CH4 concentration falls to a steady value after the main reaction has decelerated
is additional evidence that its removal is brought about by one of the carriers of
the main chain at a rate considerably faster than its spontaneous decomposition at
the same temperature.
The formation of formaldehyde and its removal from the system as the reaction
develops requires explanation, though the total amount formed is extremely small
and it is unlikely that this substance plays any direct part in the reaction. The
disappearance of formaldehyde can only be explained by its reaction with one of
the major products and the product concerned is most likely to be HCI. Both the
formation and removal of formaldehyde may be explained by the following
equliborium. CH2Cl2 + H20IHCHO + 2HC1,
which has been demonstrated to exist by Leopold & Michael (1924). Fells &
Moelwyn-Hughes have calculated the equilibrium constant to be 108 in favour of
HCI at 25 'C and since this is close to the experimental value obtained by Leopold &
Michael at 285 ?C it would appear that the reaction is thermoneutral. Increase of
HCI in the system would favour the back reaction and it can be shown that
provided this is of the second order in HCI a maximum in the formaldehyde con-
centration would be obtained as in the experiments.
The results of the flow-system experiments at increased surface/volume ratio
(figure 7) do not contribute greatly to the knowledge of the reaction. While it is
certain from the static experiments that the reaction at low pressures is-inhibited
as the vessel diameter is decreased, this effect seems to be less marked at the total
pressure of 1 atm used in the flow system. Possibly at this pressure the gas-phase
termination of chains becomes important. While the initial part of the reaction
curve is virtually unchanged the maximum rate is noticeably decreased; this may
be because the reaction rate at one atmosphere pressure is governed to some
extent by self-heating as suggested earlier, increase of surface under these condi-
tions favouring the loss of heat from the system rather than shortening the
chains. The only significant change in the formation of minor products at high
surface/volume ratio is on the part of the tetrachlorethane. This is formed in highe
ratio to trichlorethylene in the early stages as though its own dehydrochlorination.
were inhibited by increased surface, and it persists longer during the fast phase of
the reaction, possibly owing to the reduction in self heating suggested earlier. The
initial rate of formation of formaldehyde is also reduced when the reaction is carried
out at high surface/volume ratio, but the reason for this is not clear.
Finally, the mechanism given may also be used as a basis for explaining the
chlorine-photosensitized oxidation of Brenschede & Schumacher. The straight
chain part of our mechanism, reactions (1) to (4), could occur equally well at low
temperature under the influence of photochemically produced chlorine atoms,
though the branching step (5) would not be expected to occur under these condi-
tions. In this reaction, however, there are complications which lead to alternative
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The thermal oxidation of methylene chloride 211
One of us (G. W.) wishes to thank the governing body of Gonville and Caius
College, Cambridge, for the award of a Shuttleworth Research Studentship, and
the Goldsmiths Company for a Senior Studentship. The authors are also indebted
to the Shell Oil Company for a research grant to R. G. W. N. part of which was
applied as a subsistence grant to one of them (M. R. H.)
REFERENCES
I4 Vo! 250. A.
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