The Thermal Oxidation of Methylene Chloride

Author(s): M. R. Hoare, R. G. W. Norrish and G. Whittingham

Source: Proceedings of the Royal Society of London. Series A, Mathematical and Physical
Sciences, Vol. 250, No. 1261 (Mar. 10, 1959), pp. 197-211
Published by: Royal Society
Stable URL: http://www.jstor.org/stable/100858
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 The thermal oxidation of methylene chloride

BY M. R. HOARE, R. G. W. NORRISII, F.R.S. AND G. WHITTINGHAM

(Received 28 August 1958)

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.

The oxidation reactions of the halogenated hydrocarbons are of considerable

interest both in themselves and in relation to the better-known problem of the
oxidation of the hydrocarbons. Unlike the larger mono-chlorinated hydrocarbons
in which the substituent atom has simply a perturbing effect on what is otherwise
a purely hydrocarbon-type oxidation, the chloromethanes are each quite individual
in both their oxidation and thermal decomposition reactions. There is also no
clear connexion between the ease of their slow oxidation and their tendency to
undergo explosion. Methylene chloride is particularly interesting in that while it
retains a formal similarity to methane, the equivalence of hydrogen and chlorine in
its molecule places simplifying restrictions on the path of its oxidation, virtually
ruling out, for example, the participation of formaldehyde and peroxides.
Methylene chloride is well known for the ease with which it reacts with many free
radicals and atoms and its power to inhibit the oxidations of carbon monoxide
(Dixon-Lewis & Linnett I95I) and hydrocarbons (Garner et al. I956) is certainly
a consequence of this. There has, however, been little work on its combustion
proper. Harteck & Kopsch (I93I) investigated the attack of atomic oxygen on
methylene chloride qualitatively at room temperature and found that the reaction,
which is much faster than that with methane under similar conditions, leads to
carbonyl chloride and hydrogen. Later Brenschede & Schumacher in I936 studied
the chlorine photosensitized oxidation of methylene chloride and postulated a ten-
tative mechanism for this based on a chlorine atom chain. Other published work is
limited to brief descriptions of the ignition temperatures of methylene chloride + air
mixtures (U.S. Bureau of Mines Rep. Invest. no. 337, 1937).
Section 1 of this paper describes some earlier unpublished work carried out by
Norrish & Whittingham in 1942 using the static technique of pressure-time
measurement.
[ 197 1 I3-2

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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.

1. THE KINETICS OF THE REACTION

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

Methylene chloride + oxygen mixtures were found to undergo slow reaction at

temperatures above about 500 ?C; above about 600 'C explosion was possible
subject to a single well-defined pressure limit. Both slow reaction and explosion
were preceded by an induction period. In the case of the slow reaction, the rate of
pressure change increased regularly to a maximum value and then decreased
relatively suddenly, when apparently only a proportion of the reactants had been
consumed. The proportioni, like the maximum rate itself depended markedly on the
diameter of the reaction vessel (table 3). After deceleration there followed a period
of very slow reaction during which the pressure change tended to a final value. At
lower temperatures (ca. 530 ?C) the final pressure change corresponded to the

reaction CH2C12 + -22 CO + 2HC1. ()

Pressure-time curves for the reaction of different mixt
from which it may be seen that the maximum rate is much more sensitive to the
pressure of methylene chloride than to that of oxygen. The results for the reaction
at 533 0C in a vessel of internal diameter 34 mm (table 1), lead to the following
expression: d[CH2CI2]/dtmax. = k[CH2C12]20 [02109.

The initial development of the reaction could be expressed quite accurately by

the relation, Ap = Net, the parameter qS being a function of the vessel diameter as
well as the temperature and partial pressure of the reactants. Its variation with
temperature could be expressed by: 0 = 50 exp (-26 000/IRT) with the time

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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.

TABLE 1. DEPENDENCE OF RATE OF OXIDATION ON REACTANT PRESSURE

(Vessel diameter 34 mm; T = 533 'C.)

pressure CH2C12 pressure 02 maximum rate

(mm) (mm) (mm/min)
50 50 4*0
50 75 5-8
50 100 7.5
50 150 10.2
75 50 8-5
100 50 16.6
150 50 36*9

TABLE 2. THE VARIATION OF BRANCHING FACTOR 55 WITH TEMPERATURE

(Quartz reaction vessel; internal diameter 34 mm; 50 mm CH2012 +50 mm 02.)

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

simultaneous oxidation. Generally, the induction period increased with decrease

in the maximum rate.
As in the thermal decomposition reaction, the addition of small amounts of
transdichlorethylene had a marked sensitizing effect, the addition of only 1 to
100 mm of an equimolar CH2Cl2 + 02 mixture causing almost complete removal of
the incubation period. The effect of added formaldehyde was also investigated; the
addition of 1 to 5 mm of the mixture to 100 mm of equimolar CH2012 + 02 caused
a slight lengthening of the incubation period, without significant change in the
maximum rate. This is in contrast to the sensitizing effect of formaldehyde on
methane oxidation.

TABLE 3. EFFECT OF VESSEL DIAMETER ON RATE OF OXIDATION

(PcH2= 50 mm; P02 = 50 mm; T = 533 0C.)

vessel percentage
diameter maximum rate 'fast' reaction
(mm.) (mm/min) (approx.)
34 16-3 60
25 100 50
21 6.7 40
10 2 3 14
2-3 0.0 0

TABLE 4. THE EFFECT OF INERT GAS ON THE OXIDATION OF 0H2C12

(P'c2ci2 = 50 mm; P02 = 50 mm; T = 533 0C; vessel diameter 21 mm.)

pressure of
added N2 maximum rate
(mm) (mm/min)
0 4*1
50 602
100 7.9
150 10-0
200 12*2

The ignition of methylene chlo

With equimolar mixtures in the region of 650 to 800 00 a single explosion limit
was observed, which tended rapidly to higher temperatures as the pressure of the
system was reduced (figure 2). The explosion of these mixtures was characterized
by the emission of lilac-blue light and the formation of a positive pressure pulse.
The explosion limit could be expressed by the equation log1o p = A/T + B, in whic
A is a constant for the system and B varies with the composition of the mixture
and the geometry of the reaction vessel (table 5). A plot of the 'induction period'
before explosion against pressure is continuous with the curve expressing the
incubation period of the slow reaction as the system passes from explosive to
quiescent conditions (figure 3).
Increase of the partial pressure of methylene chloride in the mixture led to
a raising of the explosion limit. By juducious choice of pressure, a transitional
condition could be observed in which a pressure pulse occurred during slow reaction
without leading to complete explosion. This is similar to what has been observed

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 The thermal oxidation of methylene chloride 201

by Vanpee & Grard (I955) in methane oxidation, except that in the pr

light emission could be detected. The values of both slow reaction rates and ignition
limits were very dependent on the conditions of the vessel surface, though in both
cases reproducible values could be obtained after carrying out a number of runs
without intermittent admission of air to the vessel.

300 y cc 120g ?\b4

120 ~~~~~

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.

TABLE 5. THE IGNITION LIMITS OF METHYLENE CHLORIDE + OXYGEN MI

log1o P= AIT+B
vessel
mixture diameter
CH2C12 + 02 (mm) A B
1:3 34 5000 3.6
1:3 25 5000 3d1
1:1 25 5100 2-8

The addition of small q

explosions to the extent of doubling the ignition pressure of a 1: 3 fuel + oxygen
mixture for the addition of 5 mm NO2. This is in complete contrast to the sensi-
tizing effect which nitrogen peroxide has on the explosions of hydrogen, carbon
monoxide or methane with oxygen.

2. THE ANALYSIS OF REACTION PRODUCTS

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

about 0 01 to 0. 1 mol. 0 of the products dissolved in unreacted methylene chloride.

Figure 4 shows a representative chromatogram of the low-boiling products.
Water. Water was analyzed in a separate run in which the products were trapped
at - 78 ?C, distilled into a specially designed cell and titrated against Karl
Fischer reagent. This method was sensitive to about 0 1 mg of water.
Formaldehyde. The products of a separate run were trapped in liquid oxygen,
distilled into a detachable trap and shaken with a known amount of water. The
formaldehyde in the resulting solution was then estimated colourimetrically using

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

FIGURE 4. Chromatography of the oxidation prod

Chlorine. Treatment of the aqueous extract of the condensable products with

starch and potassium iodide gave a very weak positive reaction for chlorine. It was
not possible to determine the amount formed quantitatively, but it was never
enough to give a strongly positive starch/iodide reaction under any experimental
conditions.

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

The overall reaction curve (figure 5) is similar in shape to the pressure-time

curves obtained in the static experiments, except that its initial rise is rather less
than exponential. There appears to be a period of less than 10 s during which the
rate of HCI formation increases to the small almost constant value of the first 30 s
of reaction. Most of the reaction takes place after this point in a few seconds of
swift acceleration which ceases, in this case, when about 80 % of the HCI has been
liberated. Combining the amounts of CO and C02 formed, it is clear that the basic
reaction is: CH2C12 + 1O2 -->CO + 2HCI, the CO oxidizing secondarily at an appreci
able rate.
The principal minor product of the reaction is water, which is formed initially at
the rate of about 0-2 mol. per mol. of HCI and thereafter at a decreasing rate,
apparently unaffected by the increased formation of HCI. Trichlorethylene is
formed steadily at the beginning of the reaction (about 0 04 mol. per mol. HCO)
while tetrachlorethylene forms at an increasing rate (up to 0.1 mol. per mole of
HCI), but then begins to disappear rapidly from the system just before the point of
maximum overall velocity. Chloroform is formed initially at about 0-005 mol. per
mol. HCI but increases somewhat during the fast phase of the reaction. cis-C2H2C02
is formed initially at a rate comparable with that of chloroform and its concentra-
tion increases to a small but definite maximum at the point of maximum velocity.
Tetrachlorethylene and carbon tetrachloride appear in small amounts in the last
stages of reaction; methyl chloride, vinylidine chloride and trans-dichlorethylene
also appear in minute amounts corresponding to less than one mol. per ten thousand
of HCI. The behaviour of formaldehyde which grows during the induction period
at about 0 04 mol. per mol. of HCI only to disappear from the system as the HC1
concentration increases, is particularly interesting.

The variation of surface/volume ratio

Figure 7 shows the results of experiments carried out under conditions identical
with those of the previous ones except that the vessel used had a surface/volume
ratio almost three times as high. The maximum rate appears to be decreased
slightly without significant change in the initial part of the curve; the rates of
formation of trichlorethylene and chloroform are virtually unchanged by the
increased surface, but tetrachlorethane forms somewhat more rapidly initially and
persists longer in the system before decaying. Formaldehyde is formed at only
about half the original rate but reaches a maximum concentration and decays as
before.

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

There is a remarkable similarity between the behaviour of the oxidation reaction

and that of the thermal decomposition described in the previous paper. Thus, for
example, although oxidation takes place at distinctly lower temperatures (ca. 50 'C)
than the simple thermal decomposition, the results show that above about 550 0C
pyrolysis must occur simultaneously with the oxidation at an appreciable rate
especially when the mixture is rich in oxygen. The conditions for the flow-system
experiments, namely, an equimolar mixture reacting at 579 OT, were chosen to give

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)

FIGURE 7. The oxidation of CHI2C12 at 579 00 (high Sly).

V =C4-63; -=P08 =380mm.

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

Altogether, these similarities are sufficiently strong to raise the question of

whether the primary stages in the two reactions are identical, oxygen only inter-
vening in one of the later stages of the oxidation process. The possibility of
a distinct oxidation chain cannot, however, be ruled out, since such a mechanism
has been proposed by Brenschede & Schumacher (I936) to account for the chlorine
photosensitized oxidation of methylene chloride.
Brenschede & Schumacher found that mixtures of methylene chloride, chlorine
and oxygen reacted readily at 50 ?C when irradiated at 4360 A. As the oxygen to
chlorine ratio was increased, the oxygen-inhibited chlorination reaction gave way
to a chlorine sensitized photo-oxidation. The quantum efficiency for this was of the
order of 800 and the end products were HCI and CO. The reaction showed a long
incubation period just as in the thermal oxidation, for which the authors were
unable to account. They proposed, however, that the reaction is governed by
a straight chain with the C1O radical as a carrier. With slight modification this
could also account for the thermal oxidation:

CH2C12 + C1 -_ CHC12 + HC1,

CHC12 + 02 -> CO + HCI + C1O

ClO* + CH2C12- - CO + 2HC1 + Clb, etc.

Considerable restriction is placed on the nature of possible oxidation chains by

the stoichiometry of the reaction. The participation of oxygen atoms is ruled out,
for example, since these are known to react with methylene chloride to give
carbonyl chloride and hydrogen (Harteck & Kopsch I93i). The hydroxyl radical
seems equally unlikely to be an intermediate, since its participation would certainly
lead to water as a major product of the reaction.
In view of these restrictions the elucidation of the oxidation mechanism seems to
reduce to a choice between the Brenschede & Schumacher chain and a modified
version of the decomposition chain proposed in the preceding paper.
The most serious objection to the Brenschede & Schumacher mechanism is that
it does not provide for any delayed branching step and cannot therefore account
for the slow development of the reaction either in the photochemical or the thermal
oxidation.
It is clear, however, that the reaction is not a 'modified pyrolysis' in the simplest
sense, that is to say that carbon formed in an unperturbed decomposition chain
is oxidized subsequently in an independent process. If this were the case the
addition of oxygen would not lower the reaction temperature or affect the maxi-
mum rate. In fact the maximum rate is proportional to [CH2C12]2 [02]O9 in the
region where pyrolysis may be neglected. The dependence on the second power of
methylene chloride concentration suggests that the basic kinetic pattern is similar
to that of the thermal decomposition. Considering a general degenerately branched
scheme for decomposition, it will be seen that the ways in which oxygen may
intervene and still lead to a steady state equation compatible with the above
expression are limited. First, oxygen may not attack the degenerate branching
agent and remove it without the generation of chains; this would lead to inhibition

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 208 M. R. Hoare, R. G. W. Norrish and G. Whittinghamr

of the reaction by oxygen which is clearly at variance with experiment. Secondl

if oxygen only intervenes in the last stage in which the decomposition end products
are fornmed, it can be shown that this does not affect the overall kinetics in any way.
The only remaining possibility is that oxygen intervenes in the branching act thus
increasing the rate of generation of centres.
Applying these considerations to the mechanism for simple decomposition given
in the previous paper, we arrive at the following oxidation mechanism which may
be regarded as the most plausible:

primary chain of CH2C12 f CH2C12 + C1 -l CHC12' + HC1 (1)

decomposition 0C1C12' + CH2C12-*--> [CHCl:CHCl] + HCl + C1, etc. (2)

secondary chain of 4 [CHCl:CHCl] + Cl' > C2HC12' + HCl (3)

C2H2C12 oxidation C2HC12 + ?2 > 2CO + HCl + Cl., etc. (4)*

degenerate branching- f [CHCl:CHCl] + 02 > [H201 + CO + CC12 (5

CC12' + CH2C12 > 2CHC12* (6)

[ ~~CHCI2 2[22C4 > [CHCL CC21] (7)

1 ~~~~~~walls
termination CHC12' + Cl w-al [CHC13]- [C2C041 (8)
walls
2C1- [->C12] (9)

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

(d[CH11C12]/dt) 4k, k2k.5Pd [H 1]2

2 max. k3k7 013 k7220

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

possibilities for branching: in the presence of the high proportion of chlorine

needed for sensitization, chloroform and carbonyl chloride are certain to be pro-
duced, either of which might lead to branching reactions even at low temperatures.
Further work would be required to distinguish between these possibilities.
The ignition of methylene chloride in oxygen differs from that of methane
(Neumann & Serbinov 1932), methyl chloride (Whittingham I942) and carbon
monoxide (Hoare & Walsh I954) in that there is apparently only one explosion
limit at all temperatures. Increase in the fuel/oxygen ratio inhibits the explosion
as is the case in most systems. Although the Semenov equation for the explosion
limit is obeyed (table 5), this as usual gives little help in understanding the relative
contribution of chain and thermal effects to the explosion. The continuity of the
curves of incubation period and pre-explosion induction period against pressure as
the system passes from quiescent to explosive conditions (figure 3) shows, however,
that the build up of chains by the same mechanism as that of the slow reaction is
at least one of the conditions for explosion. The non-existence of an explosion
peninsular due to carbon monoxide ignition is not surprising in view of the fact that
carbon monoxide + oxygen explosions are markedly inhibited by both methylene
chloride itself and its product HCI (Dixon-Lewis & Linnett I95I).

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.)

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Brenschede, W. & Schumacher, H. J. I936 Z. Phys. Chem. A, 177, 245.

Dixon-Lewis, G. & Linnett, J. W. 195I Proc. Roy. Soc. A, 210, 48.
Egriwe, E. I937 Z. Anal. Chem. 110, 22.
Fells,I. & Moelwyn-Hughes, E. A. 1958 J. Chem. Soc. p. 1326.
Garner, F. H. et al. I956 Sixth Symposium (International) on Combustion, p. 802. New York:
Reinhold.
Harteck, P. & Kopsch, U. I93I Z. Phys. Chem. B, 12, 327.
Hoare, D. E. & Walsh, A. D. 1954 Trans. Faraday Soc. 50, 37.
Hoare, M. R., Norrish, R. G. W. & Whittingham, G. I959 Proc. Roy. Soc. A, 250, 180.
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Neumann, M. B. & Serbinoff, A. I. 1932 J. Phys. Chem. U.S.S.R. 3, 75.
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Whittingham, G. 1942 Thesis (part II) Cambridge University.

I4 Vo! 250. A.

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