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The slow combustion of c«/cZopentane

II. Analytical results and mechanism
By I. R . M cG o w a n and C. F. H. T ip p e r
Department of Inorganic and Physical Chemistry, University of Liverpool

{Communicated by C. E . H. Bawn, F.R.S.— Received 9 January 1958)

The products of the oxidation of c^/cZopentane in the gas phase at around 400 °C in an uncoated
vessel were water, carbon monoxide and carbon dioxide with smaller amounts of hydrogen,
methane, ethylene, propylene, cycZopentene, formaldehyde, higher aldehydes (mainly
acetaldehyde) and acids. It was confirmed that the pressure change was true measure of the
extent of reaction. The pressures of higher aldehydes and unsaturates rose to a maximum
at about the time of the maximum rate, and the variation of these maximum pressures with
initial oxygen and cj/cZopentane pressures was investigated. Addition of formaldehyde
initially had little effect on the reaction, but addition of higher aldehydes reduced the
induction period and increased the maximum rate. The CO/C02 ratio increased with
increasing temperature and cj/cZopentane pressure and was much greater with the boric-acid-
coated vessel. Also using this vessel peroxidic material was detected in the products. Higher
aldehydes were probably the substances responsible for delayed branching.
The various elementary reactions which may have occurred in the system are discussed and
a reaction scheme which can explain the products and to some extent the kinetic results is
proposed. CtycZopentylperoxy (C5H90 2) radicals were probably important both in propagating
and terminating the chains.

I n t r o d u c t io n

In part I (McGowan & Tipper 1958) the kinetics of the oxidation of cycZopentane
in coated and uncoated vessels were obtained from pressure-time curves. In this
part the results of qualitative and quantitative analyses of the system a t various
stages in the reaction are reported and the mechanism discussed.

E x p e r im e n t a l

At various stages during the oxidation taking place under some standard condi­
tions the products and unchanged reactants were removed from the vessel through
a trap cooled in liquid nitrogen and the permanent gases collected over mercury in
a burette. The liquid-nitrogen bath was replaced successively by baths containing
melting alcohol ( —120 °C) and solid carbon dioxide ( —78 °C), and two further
fractions collected. These three fractions were analyzed in a Bone and Wheeler
type apparatus. In the first fraction, oxygen and carbon monoxide were absorbed
in alkaline pyrogallol and cuprous sulphate+ /?-naphthol reagent, respectively, and
the gas left combusted in excess oxygen. In the second fraction, carbon dioxide
was absorbed by aqueous potassium hydroxide and the lower olefins by 90%
sulphuric acid, or sometimes by 80 % sulphuric acid and acid mercuric sulphate to
distinguish between propylene and ethylene. In the third fraction, aldehydes and
higher olefins were determined by absorption in 2,4-dinitrophenylhydrazine in
hydrochloric acid and 85 % sulphuric acid, respectively.
In some experiments, fractions 2 and 3 were condensed, removed in aqueous
solution and analyzed for aldehydes and unsaturates. Formaldehyde was deter-
[ 64 ]
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Theslow combustion of cyclo II 65
mined by chromotropic acid and the higher aldehydes by either (a) the argento-
metric method of Siegel & Weiss (1954), or ( the hydroxylamine method (Adkins
& Krsek 1949), which determines total ^>C=0 groups. The bromine method of
Burgoyne & Silk (1951) was used to estimate the higher olefins. The products
condensible at —78 °C were analyzed for water by titration with K arl Fischer
reagent, for acids by titration with standard sodium hydroxide and for peroxides
iodimetrically.
As well as these quantitative methods various organic spot tests (Feigl 1954)
were performed and infra-red spectrum analysis was used as described in the next
section.
The aldehyde vapours were added from traps attached to the apparatus.
Formaldehyde was generated from paraformaldehyde. Acetaldehyde, croton-
aldehyde and w-butyraldehyde were pure B.D.H. samples. The middle fractions
from a vacuum distillation of each were used.

R esu lts

Qualitative
Except where stated the qualitative tests were only performed on products of
the oxidation in uncoated vessels.
The ammonium molybdate test for primary and secondary alcohols was negative
for all fractions. The first fraction was shown to contain oxygen, carbon monoxide,
methane and hydrogen. The infra-red spectrum of the second fraction showed
peaks characteristic of carbon dioxide (4-34 olefins (3-28 /x), ethylene (10-45 /x)
and propylene (10-96 /x) (Bellamy 1954). This result was confirmed byreturning the
mixture to the analysis apparatus from the infra-red spectrometer gas cell, and
carrying out selective absorptions for these components, a new spectrum being
taken between each. Thus 85% sulphuric acid reduced the peak a t 10-96p. very
considerably, but did not affect the one a t 10-45 /x . This latter and the peak at 3-28/x
were completely removed by acid mercuric sulphate. The peak a t 4-34 /x was
unaffected, but the remaining gas was absorbed completely by aqueous potassium
hydroxide. The chromatropic acid test showed th at formaldehyde was present
in this fraction.
Fraction 3 was neutral and the infra-red spectrum showed the pressure of alde­
hydes, unsaturated compounds and q/cZopentane. The sample was treated with
selective reagents as above. 2,4-Dinitrophenylhydrazine removed peaks at 5-78
and 7-31 /x considered to be due to aldehydic ^>C=0 groups, and the resulting
spectrum bore a strong resemblance to th at of a sample of pure cycZopentene.
Treatment with 85 % sulphuric acid gave a vapour the spectrum of which was
identical with that of pure cyc/opentane. The reaction products also had a charac­
teristically pungent smell exactly like th at of cycloipentene. Thus this was probably
the main higher unsaturated hydrocarbon formed. The piperidine test on this
fraction was positive, indicating the presence of acetaldehyde.
A combined sample of fractions 2 and 3 from several experiments, stopped at
the maximum rate, was treated with dinitrophenylhydrazine, and the products

5 Vol. 246. A.
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66 I. R. McGowan and C. F. H. Tipper
separated on an alumina column (Adkins & Krsek 1949). The presence of only two
phenylhydrazones was indicated, and thus the aldehydes present in fraction 3
were probably mainly CH3CHO.
The products condensible at —78 °C were acid to litmus and the infra-red
spectrum showed the presence of an associated OH group (peak at 2-9 and
a strong peak at 5*82fx ^ C = 0 group). There was also a )/CH2 peak at 3-4^. but
none due to ))>C=C<^ or —C =C —. I t appears th at a carboxylic acid was present,
probably C4 or C5 from vapour pressure considerations.
With a boric-acid-coated vessel, only the products condensible a t —78 °C
in vacuo contained peroxidic material. Iodine was released from acid potassium
iodide in the cold, and more was formed on warming. Ferrous thiocyanate solu­
tion was turned red, but the titanium sulphate test was negative. I t is probable
th at free hydrogen peroxide was not present, but th at two organic peroxides were
formed, one being a hydroperoxide. Traces of a brown substance, probably poly­
meric in nature, condensed in the connecting tubes to the vessel during a series of
experiments.
Quantitative
Figure 1 shows the variation of the partial pressures of reactants and products
throughout an experiment under standard conditions in uncoated vessel I. In the
analysis of fraction 2 formaldehyde would presumably have been absorbed by
the aqueous KOH so th at the results for C02 were high, but the error was very
small as will be seen from results given later. The higher aldehydes and olefins
were determined by selective absorption, and the gas remaining after treatm ent
of the third fraction with 85 % sulphuric acid was taken to be cycZopentane. How­
ever, due to losses by solution, etc., the values of the pressures of this reactant
were probably somewhat low. A check determination of the amount of higher
olefins volumetrically was in good agreement.
There were no appreciable quantities of reactants consumed or of products
formed during the induction period, but afterwards the decrease in and
PCsHio and the increase in the main products H 20, CO and C02, corresponded
fairly closely to the overall pressure change. This is shown more clearly in figure 2,
despite the scatter of the points due to the inevitably somewhat large experimental
error. The overall pressure increase was therefore a good measure of the extent of
reaction, and the rate of pressure change was approximately equal to the rate of
loss of reactants. The amounts of higher aldehydes and olefins showed maxima at
around the time of the maximum rate. On the assumption th at the lower olefins
were propylene, the higher aldehydes acetaldehyde, the higher olefins cyc/opentene,
and the acids butyric, material balances were calculated. The errors due to these
assumptions probably cancelled to a considerable extent. The carbon recovered
varied through the experiment from 86 to 74 %, the hydrogen from 86 to 94 % and
the oxygen from 105 to 116%. Some loss of carbon and hydrogen was probably
due to the low values of the cyc/opentane pressure and the production of polymeric
material, and the high oxygen percentages to the estimated amounts of water
being too large.
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The slow combustion of cyclopentane. I I 67
Figure 3 shows the variation in the amounts of higher aldehydes and formalde­
hyde during an oxidation under standard conditions in uncoated vessel II. I t can
be seen th a t the am ount of formaldehyde was small and came to a very shallow
maximum towards the end of the reaction, while the higher aldehydes, determined
volumetrically, reached a sharp maximum a t about the time of attainm ent of the
maximum rate. Methods (a) and (6) gave the same result within experimental error
for the quantity of aldehyde in fraction 3, and a check on the formaldehyde

tim e (min) to ta l pressure change (mm H g)

F ig u r e 1
F ig u r e 1. V ariation in pressures o f reactan ts and products during an experim ent. Cyclo-
p en tan e pressure, 40 m m ; oxygen pressure, 80 m m ; tem p ., 400 °C; u ncoated vessel I.
(a) w ater x 0 *5, (&) carbon m onoxide, (c) to ta l pressure change, (d) carbon dioxide,
(e) o x ygen x 0 -5, ( / ) cycZopentane, (g) higher olefin, (h) higher aldehyde, (i) eth ylen e + pro­
pylen e, )j( acids, ( Jc)m ethane + hydrogen.
F ig u r e 2. V ariation o f th e individual pressure changes o f reactants and products w ith th e
overall pressure change. Cyclopentane pressure, 40 m m ; oxy g en pressure, 80 m m ;
tem p., 400 °C; u ncoated vessel I. (a) cycZopentane, (6) w ater x 0-5, (c) o x ygen x 0-5,
(d) carbon m onoxide, (e) carbon dioxide.

present in fraction 2 by method (b) agreed well with the value obtained colori-
metrically. The pressures of higher aldehyde agree reasonably well with those
calculated from the absorption method considering the different vessels. I t seems
probable th a t no appreciable quantity of ketones were formed in the reaction.
W ith a boric-acid-coated vessel the pressures of higher aldehyde and olefin also
rose to maxima (figure 3). An interesting feature of the results is th a t the olefin
concentration built up in advance of the overall pressure increase.
5-2
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68 I. R. McGowan and C. F. H. Tipper

tim e (min)

F ig u r e 3. V ariation o f th e pressures o f aldehydes and higher olefins form ed during th e

oxid ation. Uj/cZopentane pressure, 40 m m ; ox y g en pressure, 80 m m ; tem p., 400 °C.
Boric acid coated v e s s e l: (a) to ta l pressure change, (6) to ta l aldehydes x 2, (c) higher
olefins. U n coated vessel I I : (d ) to ta l pressure change, (e) higher aldehydes x 2,
( / ) form aldehyde x 5.

upper scale, cycZopentane pressure (mm H g)

low er scale, oxygen pressure (mm H g)
F igure 4 F igure 5

F igure 4 . V ariation o f th e m axim um pressures o f higher aldehyde and olefin w ith cyclo­
pentane and oxygen pressures. T em p., 400 °C; uncoated vessel II. H igher olefin:
(a) cyclopentane varied; oxygen pressure, 80 m m ; (6) oxygen varied; cyclopentane
pressure, 40 m m . H igher aldehyde: (c) as for (6), (d ) as for (a).
F igure 5. V ariation o f th e m axim um pressures o f higher aldehyde and olefin w ith tem pera­
ture. Cyclopentane pressure, 40 m m ; oxygen pressure, 80 m m ; uncoated vessel II.
(a) higher olefin, (6) higher aldehyde.
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Theslow combustion of cyclopentane. I I 69
Obviously the higher aldehydes and olefins were im portant intermediates in the
oxidation. Therefore, the variations of the maximum concentrations with condi­
tions were determined for the reaction in an uncoated vessel, and the results are
shown in figures 4 and 5. The increase in ij?cHo,max. with increasing cycZopentane
pressure was small but it increased markedly in a linear fashion with increase in
oxygen pressure. In contrast the maximum amount of higher olefin increased
rapidly with increase in i ^ 6Hio, bu t was virtually independent of PQl though it

added aldehyde pressure (mm H g)

F ig u r e 6. E ffect o f added aldehyde on th e m axim u m rate and induction period o f th e o x id a ­
tion. CycZopentane pressure, 40 m m ; oxygen pressure, 80 m m ; tem p., 400 °C; uncoated
vessel I I. (a) Form aldehyde, (6) acetaldehyde, (c) w-butyric aldehyde, (d) crotonaldehyde.

decreased slightly a t higher pressures. I t also increased with increasing temperature,

the overall activation energy being about 4 kcal/mole. However, i^cHo.max.
actually decreased with increase of temperature, the Arhenius plot yielding an
overall activation energy of —4 kcal/mole. The dependence of the maximum
amount of higher aldehyde on conditions was very different from th a t of the
maximum formaldehyde concentration in the slow combustions of cyclopropane
and methanol (McEwan & Tipper 1953; Bell & Tipper 1956).
The importance of the higher aldehydes as intermediates in the oxidation was
further shown by the addition of various of these compounds initially. The results
are shown in figure 6. Whereas formaldehyde had little effect on the maximum rate
or the induction period, small quantities of acetaldehyde, crotonaldehyde and
w-butyric aldehyde increased pmax and reduced 6 considerably. 6 or 7 mm of
CHgCHO or C3H 7CHO caused the reaction to commence at nearly the maximum rate.
There were relatively large quantities of carbon dioxide formed during the
oxidation in an uncoated vessel, the ratio C0/C02 being much greater than found
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70 I. R. McGowan and C. F. H. Tipper

in the products of the slow combustion of paraffins (e.g. Rust & Collamer 1954).
The variation with temperature and cycfopentane pressure of the amounts of CO,
C02, the lower olefins, and methane + hydrogen are shown in the table and in
figure 7.

cycfopentane pressure (mm H g)

F igure 7. V ariation w ith cycZopentane pressure o f th e CO/COa ratio (6) and o f th e pressure o f
eth ylen e + propylene (a) at th e end o f th e oxidation. O xygen pressure, 80 m m ; tem p.,
400 °C; uncoated vessel II.

Table 1. Variation with temperature of the pressures of CO, C02

C2H4+ C3H 6 and CH4+ H 2 at the end of the reaction
pressure (mm)
tem p. A
O
toO
O
O

<°C) c 2h 4+ c 3h 6 ch 4+ h 2 C4/CO!
370 25-6 17-2 2-5 21 1-49
400 25-9 16-5 2-7 (5) 2-3 1-58
438 25-8 15-4 3-8 2-7 1-68

The C0/C02 ratio increased with increasing temperature owing to a decrease in

the amount of carbon dioxide formed, and the amounts of the other products also
increased. The ratio and the amount of lower olefins also increased with increase of
cycZopentane pressure. I t may be noted here th at when 10 mm CO was added
initially to a *standard ’ reaction mixture the amount of carbon dioxide formed a t
the end of the oxidation was not increased. W ith boric-acid-coated vessel, however,
the carbon dioxide produced was markedly less. Under standard conditions the
CO/C02 ratio at the end of the reaction was 5*5.
A few quantitative analyses were performed on a mixture of 150 mm C5H 10 and
200 mm 0 2 undergoing slow oxidation in the boric-acid-coated vessel a t 252 °C
(Pmax. ~ 13 mm/min, d~50 min). The CO/C02 ratio a t the end of th
3*6. The concentration of ‘peroxides’ reached a maximum of 3-6 mm somewhat
later than the time of attainm ent of the maximum rate, and then decreased rapidly.
The amount of higher olefin was a maximum (approx. 8 mm) a t the time of the
maximum rate. When one mixture exploded owing to the temperature accidently
rising to 255 °C, the higher olefin pressure in the products was 34 mm. Only traces
of peroxide were found in the products of the oxidation a t temperatures above the
cool-flame limit.
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The slow combustion of cyclopentane. I I 71

D iscussion
I t is very unlikely th a t any thermal decomposition of cycZopentane occurred
under the conditions used in this work since it is only detectable a t temperatures
above 500 °C (Kiichler 1943).
The kinetic results reported in part I showed th a t the oxidation was a chain
reaction involving delayed branching. The results recorded in the last section
indicate th a t a t any rate in the ‘high-tem perature’ range the intermediates
responsible for the branching were aldehydes higher than formaldehyde. Possibly
some branching was due to peroxides a t 250 °C in a boric-acid-coated vessel, but
no definite conclusion can be drawn from the available data.
Probable elementary reactions making up the chain will now be discussed,
bearing in mind th a t they must be of a relatively simple nature, must explain the
formation of the products and if possible the kinetic results (Tipper 1957).
The primary initiation reaction was probably

C5H10 + O2 = C5H 9+ HO2,

of the type usually suggested. However, after the induction period the loss of
cycZopentane will have been due to attack by the atoms and free radicals present in
the system, i.e.
C5H10+ X==C5H 94-XH. (a)

The methane and hydrogen probably were formed at least partly by this reaction
(X = CH3 or H), but the small amounts show th a t the removal of hydrocarbon in
this way was slight. The activation energy of the reaction of cycZopentane and
methyl radicals is 8-3 kcal/mole and so the increase of the methane yield with
temperature indicates th a t other reactions of the CH3 radicals, e.g. with oxygen,
had a lower activation energy. This seems probable. Most of the water was probably
produced by hydrogen abstraction by OH radicals. I t is likely th a t H 0 2 radicals
were present in the system (see later) and also took part in reaction (a). The C—H
bond dissociation energy in cyc/opentane may be calculated from the activation
energy of hydrogen abstraction by methyl radicals to be approximately 93 kcal/mole
(see Bell & Tipper (1956) for method). Reaction (a) would therefore be exothermic
with CH3, H or OH and only 4 kcal/mole endothermic with H 0 2 (see Tipper (1957)
for general discussion of such reactions).
The cydopentyl radicals would have reacted with oxygen to give cycfopentyl-
peroxy radicals, and these would have been formed in an excited state since they
would have possessed the energy released in the association. However, owing to
their size they would have been unlikely to have dissociated or to have been
deactivated by collision immediately, since the excess energy would have been
distributed over many degrees of vibrational freedom. Possibly the excited
•CH—0—
radicals possessed a ring structure,CH2 ^CHa. However, owing to the
UH2---- ch2
high-energy content somewhat complicated breakdown reactions may have been
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72 I. R. McGowan and C. F. H. Tipper

possible, and it has been thought best to consider the various processes involving
C5H90 2 (and alkyl radicals derived therefrom) under the following headings.

Carbon dioxide formation

The unusually large amounts of C02 formed at 400 °C in an uncoated vessel
suggests that some may be produced directly from C5H 90 2 radicals, i.e.
„ *CH—0 -
XCH2= toC4H9+ 0 0 2. ib)
&
/
CH,---- -CH

Burgoyne & Silk (1951) also found relatively large quantities of C02in the products
of methylcycZopentane oxidation in Pyrex vessels. The much greater C0/C02 ratio
with the boric-acid-coated vessel indicates th at reaction (6) was mainly or com­
pletely heterogeneous, a Pyrex surface being an effective catalyst but not a boric-
acid surface.
Olefin formation
In the high temperature range the production of olefins with the same number of
carbon atoms as the original fuel has recently been shown to be important, and
there is strong evidence th at they are formed by the splitting off of H 0 2 from the
appropriate R 0 2 radicals or by direct reaction of -R+ 0 2 (Tipper 1957), e.g. in this
system C5H ,0 2* = C5H8+ H 02 or C5H„ + 0 2 = C5H8+ H 0 2. (c)
Some w-butyl radicals produced in reaction (6) might also have reacted with oxygen
in a similar way giving butene, which would have been determined as higher olefin.
However, w-butyl radicals readily decompose a t above 350 °C
wC4H9 = C2H5+ C2H4 (McNesby, Drew & Gordon 1956), (d)
and then some of the ethyl radicals might have given more ethylene by a similar
reaction to (c). Other reactions of C5H 90* giving olefins which can be envisaged are
C6H 90 2* = C02+ CH3+ C3H6 or CO + OH + 2C2H4, (e)
but the reactions (d) and (e) could only have been of minor importance since the
yield of lower olefins was small.
The early build-up of higher olefin in the oxidation in the boric-acid-coated
vessel may have been connected with the reduction in importance of reaction (b)
forming C02. Possibly reaction (c) took place to some extent on the acid surface.

Aldehyde formation
I t is very probable th at w-alkyl radicals may react with oxygen a t around
400 °C to give aldehydes as well as olefins, i.e.
CnH2«+i + 0 2 = CwH2n+1• 0 2 = Cw_1H2n_1• CHO + OH (Tipper 1957). (/)
Thus any methyl, ethyl, w-propyl and w-butyl radicals present in the system
would have given formaldehyde, acetaldehyde, propionaldehyde and w-butyric
aldehyde, respectively. The fact th at the yield of lower olefins increased with
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The slow combustion of cyclo I I 73
increasing tem perature and cycZopentane pressure suggests th a t there was com­
petition between radical decomposition reactions, olefin formation by hydrogen
abstraction by oxygen, and aldehyde formation by reaction (/), the latter having
the lowest activation energy which seems probable.
Ring splitting between various of the CH2 groups in the C5H 90* radical could
give formaldehyde, acetaldehyde, or n -propionaldehyde, e.g.

CHp CH8=C H 20 + CO + C3H , or CH3CHO+CO + C2H 5 or C ^ C H O + C O + CH,,. (g)

CH2------- CH2

However, most of the relatively small amounts of formaldehyde were probably

formed by oxidation of the higher aldehydes via reaction (/) 1), and reactions
(g) and (/) cannot have been the sole or even the main source of these higher
aldehydes for two reasons. First, the radicals CH3, C2H 5, C3H 7 would have formed
methane, formaldehyde, ethylene, etc., as well as other aldehydes. The yields of
these substances were very small and other reactions probably gave lower olefins
or alkyl radicals. Secondly, the kinetic results discussed later suggest th a t the
dependence of -pRCHo.max.on experimental conditions can only be explained on the
assumption th a t the formation of higher aldehydes was mainly due to the reaction
of C5H 90 2 radicals with oxygen although with some contribution from reaction (g).
Thus the following sequence of steps was probably an im portant feature of the
mechanism:

• CH— O—O *OOCH— O-j-O • 0-4-0CH

/ \ / • \ v x \ w
CH, c h 2+ o2= c h 2 c h ,= x c h , CH2 = 2 CH3CHO+ CO + OH.
V
ch, -CHa
\ CH, /
-CH,
\ CH, -CH,

Reaction ( h)is very exothermic, b u t if the heat of reaction was carried away by
the acetaldehyde molecules there can have been little straight decomposition to
give methane and carbon monoxide.

Hydrogen abstraction
The peroxidic material in the products of the oxidation in a boric-acid-coated
vessel probably included q/cZopentylhydroperoxide formed by hydrogen abstrac­
tion by C5H 90* radicals from cycZopentane, higher aldehyde or higher olefin, these
being the only hydrogen-containing compounds present in reasonable concentration
in the system. The reaction with aldehyde, i.e.
C5H 90 | + JRCHO = C5H 9OOH + ECO (
would probably have been the most rapid because the dissociation energy of the
aldehydic C—H bond is much less than th a t of C—H bonds in hydrocarbons
(Szwarc 1950). I t appears from kinetic evidence th a t the oxidation of higher
aldehyde in the system was mainly due to the above reaction. In the uncoated
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74 I. R. McGowan and C. F. H. Tipper

vessel, therefore, any hydroperoxide was probably destroyed rapidly at the walls.
If a part underwent the simple rearrangement

= CH3CH2CH2CH2COOH,
CH2-------CH.

this would account for the acid formed and its steady accumulation as the oxida­
tion proceeded.
I t is now necessary to consider briefly the further oxidation of the higher alde­
hydes. The main reaction resulting in aldehyde removal would have been hydrogen
abstraction by various radicals present in the system, e.g. reaction (i). However,
branching by these intermediates was probably due to reaction with oxygen, e.g.
CH3CHO + 0 2 = CH3CO + h o 2.
Studies of acetaldehyde oxidation indicate th at this is the primary initiation step
and Combe, Niclause & Letort (1955) have calculated from their results th a t it has
an activation energy 24 + 4 keal/mole. The carbonyl radicals would have decom­
posed readily in the high temperature range, e.g.
CH3CO = CH3+ CO,
but if also some carbon dioxide was formed by their reaction with oxygen, i.e.
ECO + 0 2 = C02+ products,
then the increase in C0/C02 ratio with increasing temperature and cydopentane
pressure is explained. I t is hoped to discuss CO and C02 formation during slow
combustion and the elementary steps involved in the above process elsewhere.
The variation of the oxidation rate with temperature may now be considered in
more detail than in part I on the basis of the elementary reactions proposed. The
negative temperature coefficients of the rate observed using KC1- and NaOH-coated
vessels were probably due to the reaction of C5H 90 2 radicals giving aldehydes,
which may have led to branching, being replaced by reaction (c), which was a non­
branching step, as the temperature was raised. The difference in the minima in the
rate-temperature curves for the oxidation in boric-coated and uncoated vessels may
have been connected with the reduced destruction of peroxide on the acid surface—
peroxides appear to be important in cool-flame formation—and to some extent to
the fact th at some C5H 90 2 radicals in the uncoated vessel decomposed hetero­
geneously to give C02.
In order to be able to provide some explanation of the kinetic relations the
following simplified reaction scheme is proposed:
C5H 10+ X = C5H 9+ XH (1)
c 5h 10+ C5H 90 2 = C5H 9+ C5H 9OOH ( 2)

c 5h 9+ o 2 = c 5h 9o 2 (3)
> primary chain
C5H
5n 90
9u 22 = C5H 8 + X (4)
C6H 90 2 = ECHO + .X (5)
C5H 90 2+ 0 2 = ECHO + X ( 6)
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Theslow combustion of cyclopentane. I I 75
-RCHO + 0 2 = X +products branching,
i2CH0 + C5H 90 2 = products + X | (8)
ECHO + X =products + j (9)
C5H 8+ X = oxidation, (10)
C5H 9OOH = inert (surface), (11)
C5H 90 a + 0 2 = inert) (12)
} termination,
X +0 2 = inert J
X represents other radicals than C6H 90 2, e.g. OH, H 0 2.
Since the concentration of higher aldehyde rose to a maximum a t about the time
of attainm ent of the maximum rate, ignoring the relatively small amount removed
by reaction (7) and also any removed by reaction (9),

d(i?CHO)m, r = fc6(C6HA)mr + ^ ( ^ 0 ^ (0a)m r

- ^ H A U ^ C H O ) ^ = 0;
therefore (72CHO)max< = (l/k8) {k5+ &6(02)mx}.
Provided the oxygen left a t the time of the maximum rate was proportional to the
initial concentration, this relation agrees with the experimental dependence of
-Fjjcho, max. on T0 . The effect of reaction (9) would be to cause the maximum
aldehyde concentration to vary with the cycZopentane pressure, but figure 5 shows
th a t this method of aldehyde removal was only of minor importance. The negative
activation energy for (_RCHO)max would then indicate th a t reaction (8) had a higher
activation energy than (5) or (6).
For the higher olefins a t the time of the maximum rate
r ^'lo('^Om .r.(^5^8)m ax.•

I t must now be assumed th a t the chains were long and th a t there were stationary
concentrations of X , C5H 90 2 and C5H 9 radicals a t this stage of the oxidation. Then
^i(-^)m.r.(C5H10)mr + &2(C5H 90 2)mr (C5H 10)mr = &3(C5H 9)m r (02)mr
and ^3(^-'5-^-9)m.r.(02)in.r. ^2(^5^9^2)m.r. (^“'5^-10)m.r. “I” ^'4(^5^9^2)111.r.
+ r+ r(02)mr
+ £8(UCHO)max (C5H 90 2)mT ;
therefore &i(A)mj,(C5H 10)mr = (&4 + 2 k+ 2&6(02)
and
^4(C5H90 2)mr = ^io(C5H 90 2)mr{yb4 + 2k 5+ 2&6(02)mrJ (C5H8)inax /A;1(C5H10)rn_r/
Thus (C5H8)max. = kx&4(C5H 10)m r/&10{&4 + 2k5 + 2&6(02)m r}.
Therefore, provided th a t the cycfopentane concentration at the maximum rate was
also proportional to the initial concentration, the experimental variation of the
maximum amount of higher olefin with reactant pressures is reasonably adequately
explained. I t must be noted, however, th a t if a reaction between C5H 90 2 radicals
 Downloaded from http://rspa.royalsocietypublishing.org/ on January 23, 2018
76 I. R. McGowan and C. F. H. Tipper
and C6H8 was included in the scheme then an expression for (C5H8)max could not
be derived.
The maximum oxidation rate was proportional to the maximum rate of loss of
cycZopentane and
[d(C5H10)j
^1( X )m.r.(^5^10 )m.r. + ^(^HgCynj r>(C5H10)mr
l d£ jmax.
k x ^ 2 (^ 5 R lo )m .r.(^ )m .r.
^1(^)m.r. (^R-IO )m.r. JcA+ 2k5+ 2^6(02)m.r.
from equation (A).
Now fresh radicals were injected into the system by reaction (7) and radicals were
removed from the system by reactions (12) and (13); therefore
k-j (-RCHO)max (0 2)mr = yfc12(C5H 90 2)m.r.(02)m.r. + ^i3(A)m.r.(02)m.r.-
Substituting for (i?CHO)max> and (C5H 90 2)mr_
,y\ _ ^7 (^ 5 + ^6(G2)m.r.} + 2fc6(Q2)mr}
m'r" k8{kx^ 1 2 (^5^10)m.r. 'b + ^^5 b 2^6(02)mr.}
Substituting this in the expression for the rate and rearranging, it is found th at the
theoretical form of dependence of pmax on reactant concentrations is
A d C ^ o ) + A2(C5H10)2+ A3(C5H10)(O2) + A4(C5H10)2(O2) + A 5(C5H 10)(O2)2
Pmax- A 6(C5H10) + A7(O2) ’
where K x to K 7 are constants involving the various velocity constants.
This expression agrees to some extent with the experimental rate variation in
th at there are terms in (02)2 and (C5H10)2 but the rate varies linearly with (02) or
(C5H10) for high oxygen—low cycZopentane pressures or vice versa.
If either reaction (12) or (13) had not contained oxygen as a reactant, a term in
(02)3 would have appeared in the theoretical rate expression. Thus the termination
steps appear to be the most probable that can be postulated under the circum­
stances. I t is likely that (13) was heterogeneous, the radical involved being H 0 2.
This would account for the effect of surface and added nitrogen, since there is
strong evidence th at heterogeneous termination of chains in the ‘high-tempera­
ture ’ slow combustion of other compounds is due to H 0 2 radicals (Hoare & Walsh
1955; Bell & Tipper 1957). However, since the effect was relatively small, reaction
(12) must have been homogeneous and may have occurred thus:
•CH—O—O -OOCH—O—O
/
ch2
\^ c h . + o ^ c/h , \^ c h 2= o 2+ h 2o 2+ c6h 7-,
c h 2------- c h 2 c h 2------- c h 2

the radical C5H 7 being resonance-stabilized and unable to continue the chain. I t
has been suggested that the retardation by olefins of their own oxidation (Bawn &
Skirrow 1955) was due to the formation of resonance stabilized radicals.
Although variations of the mechanism proposed might be suggested, it is con­
sidered that the elementary reactions and the general scheme put forward do
 Downloaded from http://rspa.royalsocietypublishing.org/ on January 23, 2018
Theslow combustion of cyclopentane. I I 77
account for many if not all of the analytical and kinetic results in a reasonable
manner. I t is not to be expected with such a complex system th a t every feature
can be fully explained.

The authors thank Professor C. E. H. Bawn, F.R.S., for helpful discussion, and
the University of Liverpool for a scholarship to one of them (I.R.McG.).

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