The Mechanism of The Acetaldehyde Pyrolysis

The Mechanism of the Acetaldehyde Pyrolysis
Author(s): K. J. Laidler and M. T. H. Liu

Source: Proceedings of the Royal Society of London. Series A, Mathematical and Physical
Sciences, Vol. 297, No. 1450 (Mar. 7, 1967), pp. 365-375
Published by: The Royal Society
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The mechanism of the acetaldehyde pyrolysis
BY K. J. LAIDLER* AND M. T. H. Liu
Department of Chemistry, The University of Ottawa, Canada
(Communicated by F. S. Dainton, F.R.S.-Received 29 June 1966)
Previous work on the acetaldehyde pyrolysis is shown to be vitiated by the presence, in the
acetaldehyde, of impurities, mainly ethanol and crotonaldehyde. The reaction has been
reinvestigated with the use of acetaldehyde, prepared from paraldehyde, which is free from
these and other impurities. On the basis of a study of the kinetics of formation of the
major products (methane and carbon monoxide) and of a number of minor products
(hydrogen, acetone, propionaldehyde, ethane and ethylene) a reaction mechanism is pro-
posed. This includes all of the reactions in the original Rice-Herzfeld scheme, together
with a number of other elementary processes, in particular
CH3 + CH3CHO -* CH4 + CH2CHO.
The decomposition of the radical CH2CHO into
CH2CO
and H provides an additional source
of hydrogen, the rate of production of which is therefore not a measure of the rate of the
initiation process. Acetone is believed to arise mainly by the reaction
CH3 + CH3CHO
-*
CH3COCH3 + H,
and only to a negligible extent by the combination of CH3 and CH3CO. The main chain-
ending step is concluded to be
CH3 + CH3-*
C2H6,
with a small contribution from
CH3 +
CH2CHO
-*
CH3CH2CHO.
The work provides further evidence for the falling off, at low pressures, of the second order
coefficient for the combination of methyl radicals. Rate constants for various elementary
processes are deduced from the rates of formation of the various products, and are shown
to be consistent with values obtained directly.
INTRODUCTION
In spite of a considerable amount of work on the thermal decomposition of
acetaldehyde, many details of the mechanism have remained obscure and confusing.
Some of the results are consistent with the original mechanism of Rice & Herzfeld
(I934):
C
H3CH0 CH3
+0CH0,
CHO CO+1H,
H + C13H
0 -
1CH3C0+ H2,
CH3+CH3CHO
-0
CH4
+ CH3C0,
CH300 CH3
+ C0,
CH3
+0CH3
C-26
This scheme successfully accounts for the following features of the reaction:
(1) The main reaction products are methane and carbon monoxide; these are
produced in the chain-propagating steps.
*
Now at the Chemical Laboratory, University of Sussex, Falmer, Brighton (1966-67).
[ 365 ]
366 K. J. Laidler and M. T. H. Liu
(2) The order of the reaction is three-halves; this is explained if the order of the
termination reaction is one greater than the order of the initiation reaction (e.g. if
initiation is first order and termination is second order).
There are, however, a number of experimental results that cannot be reconciled
with this mechanism, such as the following:
(1) According to the mechanism the only minor products should be hydrogen and
ethane. In addition, however, significant amounts of acetone, propionaldehyde
and ethylene are formed (Trenwith I963; Dexter & Trenwith I964). Indeed Dexter
& Trenwith (I964) found that the initial rate of acetone production is much greater
than that of ethane production, from which they concluded that the methyl
radical combination cannot be the main termination step.
(2) Eusuf & Laidler (I964), in agreement with the results of Bril, Goldfinger,
Letort, Mattys & Niclause (I950), found that the overall rate of reaction is reduced
by the addition of inert gases, and from this they concluded that the methyl radical
combination must be in its pressure-dependent region. The recent work of Quinn
(I963) and of Lin & Back (I966) has, however, indicated that the methyl radical
combination should be in its second order region under most of the conditions used
in the acetaldehyde pyrolysis. There is also some confusion on the experimental
side about inert gas effects; Niclause (I954) later reported that there was no effect
on the overall rate, and Dexter & Trenwith (I964) found an effect on the rates of
both the initiation and the termination reactions, but no effect on the initial overall
rate.
(3) Trenwith (I963) found that the hydrogen production was second order in
acetaldehyde. If the Rice-Herzfeld scheme is accepted this can only mean that
initiation is second order in acetaldehyde; this, however, leads to the incorrect
overall order if the termination process is taken to be second order.
(4) Eusuf & Laidler (I964) found the rate of ethane production, which on the
basis of the mechanism must be equal to the rate of the initiation process, to be
second order in acetaldehyde and to be increased by the addition of inert gas. Again,
this result is inconsistent with the overall order if the termination reaction is second
order.
It is evident that several of the reported experimental results are inconsistent with
the Rice-Herzfeld mechanism, and that some of these (particularly those relating
to inert gas effects) are mutually inconsistent. The present work was undertaken
with the object of resolving these difficulties. It was suspected that some of the
experimental anomalies, especially those relating to the rates of production of
minor products, were due to traces of impurities in the acetaldehyde employed,
and great care was therefore taken to test, by vapour phase chromatography, nuclear
magnetic resonance spectroscopy and mass spectrometry, for such impurities
and to work with samples of acetaldehyde that were substantially purer than had
previously been employed. When this was done the kinetic results were somewhat
different from those previously obtained. They could be reconciled with a scheme
of reactions based on the original Rice-Herzfeld mechanism but including a number
of important additional reactions.
The mechanism of the acetaldehyde pyrolysis 367
EXPERIMENTAL
Materials
Acetaldehyde obtained from Eastman Organic Chemicals and from the Matheson
Company, and purified by a number of bulb-to-bulb distillations, showed identical
kinetic behaviour, even as far as the minor products were concerned. However,
the fact that there was a high initial rate of ethylene production, as found by Tren-
with (I963), led to the suspicion that ethylene was being formed from an impurity.
This was confirmed by pyrolysing partially decomposed acetaldehyde, which
produced ethylene at a considerably lower rate. Vapour phase chromatography and
nuclear magnetic resonance studies indicated that the main impurities were ethanol
and crotonaldehyde. These impurities are not removed from the acetaldehyde
by distillation.
It was found that impurities were not present in acetaldehyde prepared from par-
aldehyde, and this was the material used in the remainder of the investigations. East-
man Research Grade paraldehyde was distilled, and the fraction of b.p. 1240C
was collected. This was distilled under nitrogen with addition of a small quantity
of concentrated sulphuric acid, and acetaldehyde boiling at 21 ?C was collected and
purified by trap-to-trap distillation and degassed at - 160 TC to remove traces of
oxygen. It was stored at -78 ?C and redistilled each time before use. No trace of any
impurity in this material was revealed by vapour phase chromatography, nuclear
magnetic resonance spectroscopy or mass spectrometry.
Apparatus
The decomposition was carried out in a conventional static system. The reaction
vessel was a quartz sphere 515 ml. in volume, with a S/ V ratio of 0 6 cm-1, enclosed
in a furnace consisting of an electrically heated steel cylinder 15 cm thick. The
temperature of the vessel was controlled to within 0-2 degC by means of a thermo-
electric thermoregulator. The temperature was measured using a chromel-alumel
thermocouple.
Procedure
Before each experiment the system was evacuated to a pressure of 10-5mmHg.
At the end of each run the products and reactant were fractionated through traps
at 130,
- 150 and - 210 'C. Acetone was measured by transferring all the conden-
sable products to a sampling U tube, followed by gas-chromotographic analysis
on a 5 m column of 20
% tetraethylene glycol dimethyl ether on Chromosorb P
(hexamethyldisilazane treated) at 30 'C. The area of the acetone peak was measured.
The column was calibrated by using a measured amount of acetone mixed with an
appropriate quantity of the reactant used in the pyrolyses. The non-condensables,
hydrogen, carbon monoxide and methane, were measured in a gas burette and
analysed on a 4m 100mesh silica-gel column maintained at 0?C. Analysis on
a 1 m silica-gel column at 30 'C showed that the - 210 0C fraction contained
ethane, carbon dioxide, ethylene and the residual methane. The volumes of these
gases were also measured by gas burette. Helium was used as carrier gas in all cases.
RESULTS AND DISCUSSION
Rates of production of the major product methane and of the minor products
hydrogen, acetone, ethane, ethylene, propionaldehyde and carbon dioxide were
measured at 523 0C at pressures from 11 to 558 mmHg. Some results are shown in
figure 1, and initial rates are given in table 1. These rates are the averages from
06
-
O |3 COCH3
0
04
-
?
0~~~~~~~
0
0-2
0
CA
CH3CH2CHO
7x
0 200 400 600
time
(see)
FiGIJRE 1. Products of
pyrolysis
at 523 'C; acetaldehyde pressure
=117
mmllg.
TABLE 1. INITIAL RATES OF PROD-UCT FORMATION
(T
= 5 23 'C; all rates are in moles ml.
-
s
-1)
pressure
of
acetyldehyde
(mmllg)
1010
vC4
1013
VH 2
1013
V0113000113
1013 V
C2116
1013
VC2H15CHO0
11I 1.10 /022
20 2*28 5.6 -0-54
30.5 3.50 0
_ 095
40 6-20 13*6 -1.65
55 10-0 224 64 5 2631
77 17.5 32.5 15*6 3-8 cca. I- 5
117 321 6 61P2 27? 2 5*9 oct. 1
5
150 48.0 82*5 37.5 7.3 oct. 2
195 71T 0 129 57.5 9R5 Oc. 3
292 129.0 230 -157
558 3600 555 - 307
3 to 8
experiments,
and were obtained not from initial
slopes
but
by extrapolating
rates to zero time. It is to be seen from
figure
1 that for the
hydrogen production
there is no
sign
of the induction
period
found
by
Trenwith
(1963).
There is also no
The mechanism of the acetaldehyde pyrolysi,s 369
initial rapid formation of ethylene, which was found by Trenwith (i 963) and by us
when we used impure acetaldehyde.
The order of methane production was
3
at pressures above 100 mmHg, and
some falling off of the rate constant was noted at lower pressures. The
-a order
rate constant was 0 91 ml. mole' s-', to be compared with 0 99 obtained by Eusuf
& Laidler (I964) and 0.59 ml.i mole- s-1 obtained by Letort
(I937).
To explain these results we suggest the following mechanism, which is the
Rice-Herzfeld scheme to which a number of reactions have been added:
[1] CH3CHO CH3+CHO,
[2]
CHO CO + H,
[3]
H +
CH3CHO H2
+ CH3CO,
[4] CH3
+
CH3CHO CH4
+ CH3CO,
[5] CH3CO CH3 + CO,
[6] CH3 +CH3CHO CH4 + CH2CHO,
[7] CH2CHO CH2CO
+ H,
[8] CH3
+
CH3CHO CH3COCH3
+ H,
[9]
CH3
+ CH3 C2H6,
[10]
CH3+CH2CHO CH3CH2CHO.
Reaction [1], the initiation reaction, is concluded to be in its first order region. The
rate of ethane formation is significantly greater than for propionaldehyde forma-
tion, so that the main termination step is [9]; a variety of evidence (Quinn I963;
Lin & Back I966) has shown that this reaction is second order under the usual
pyrolysis conditions.
First order initiation and simple fl,8 termination (Goldfinger, Letort & Niclause
1948) lead to
3
order kinetics, in agreement with the results of many workers for
this reaction; in the present investigation it was confirmed that the methane and
carbon monoxide production is strictly
3
order in acetaldehyde. If the minor
termination step [10] is ignored the rate of disappearance of acetaldehyde, approxi-
mately equal to the rates of formation of carbon monoxide and methane, is found to
be VCu3CHO
= Vco = VI = 14(kl/kg)1 [CH3CHO]3. (1)
From the overall rate constant of 0-91 ml.1 mole s-1 it is possible
to calculate
kc, by using the value of k4 (see below) and the
kg
value of Shepp (I956); the result is
ki
= 2-5 x 10-7 s-1.
Ethane production
The logarithm of the rate of ethane formation is plotted against the logarithm
of the acetaldehyde pressure
in figure 2. The order is unity at the higher pressures,
but there is a significant falling off from linearity at pressures below 80 mmHlg.
If reaction [4] is the only source of methane and reaction [9] the only source of
ethane l
(
ks
= Ve
2H[CI3CHO].
(2)
24 lCI24
24 Vol. 297. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~A.
X / 30
bID
0
- _
-1 42
IIII I I I
1 2 3 10 15 20 25
log10 (P mmHg) log , (P mmHg)
FIGURE 2 FIGURE 3
FIGURE 2. Plot of log10
VC2R6
against log10
PC113CRO
(mmHg); T =
523 ?C. The dotted line cor-
responds to log10 v1, with k1 equal to 3-0 x 10-7 s-1.
FIGURE 3. Plot of
log1o
(kQ/k4)
against
log1o
P (mm Hg); T = 523 ?C.
Figure 3 shows a plot of the logarithm of the right hand side of this equation against
the logarithm of the acetaldehyde pressure; again the falling off of
kg
at low pres-
sures is observed. In the ethane pyrolysis at 550 ?C Lin & Back (i 966) have observed
a falloff of the rate coefficient for the methyl radical combination below about
200 mmHg pressure, while in the mercury-photosensitized decomposition of
dimethyl ether at 200 to 300 ?C Loucks & Laidler (I966) have observed a falloff
at 100 mmHg pressure. It appears that for this reaction acetaldehyde is a somewhat
more efficient third body than ethane or dimethyl ether.
The high pressure value of k4/k , obtained from (2), is consistent with values of
k4 and
kg
obtained directly. Thus use of the 1c9 value of Shepp (I956) together with
our results gives rise to 8-6 x 109 moles ml.-1 s-1 for k4 at 523 ?C, in excellent agree-
ment with the value of 8-7 x 109 calculated at this temperature from the data of
Brinton & Volman (I 952). The proposed mechanism is therefore entirely consistent
with the observed relative rates of formation of methane and ethane.
The steady state equation for the total radical concentration is
V=V +
vvo (3)
whence
vi
=
VC2H6
+
vC2H5CHO-
(4)
The half-shaded circles in figure 2 denote the values of Vc216 to which have been
added the rates of propionaldehyde production. The sum of these rates corresponds
to a k1 value of 3 0 x 10- s-1, which agrees very well with the value of 2-5 x 1O-7 S-1
deduced above from the overall rate.
Acetone production
Trenwith (I963) found that the rate of acetone production was greater than the
rate of ethane production, and the present work confirms this. Trenwith assumed
that acetone is formed by the reaction
[11] CH3CO
+
CH3 ->CH3COCH3,
which he therefore concluded to be the main termination step. Eusuf & Laidler
(I964) pointed out that the overall kinetic behaviour cannot be explained if this
is the main termination step, and suggested that acetone is formed by reaction [8],
a reaction which may involve an intermediate of structure
H
H3C-C-O
CH3
There are other objections to reaction [11] as an important termination step.
If this reaction occurred, acetyl radicals would dimerize with the formation of
biacetyl, and a rough estimate shows that the rate of formation of biacetyl should
be comparable to that of acetone. Such amounts of biacetyl would be easily detect-
able using the techniques of the present investigation, but none was found. It is
also possible to estimate the relative concentrations of CH3CO and CH3 in the reac-
tion system. The steady state condition leads to
[CH3CO] _ k4[CH3CHO]
(5)
[CH3] k5
where k5 is a constant
(kcr)
at high pressures and becomes proportional to pressure
(kO[CH3CHO]) at low pressures. O'Neal & Benson (I962) have obtained values of
ko and k?, and the use of these values, together with our value of k4 or those of
Kerr & Calvert (I965) and Brinton & Volman (I952), leads to the conclusion that
[CH3CO]/[CH3] is 10-2 to 10-3 under the conditions of the present experiments. The
methyl-methyl combination will therefore be by far the most important termination
process.
This conclusion is supported by a consideration of the rates of formation of
methane found in the present experiments. If acetone were formed mainly by
reaction [11] it can be shown that
VCl3coH3 kk cll 4cH (6)
k3k~
0114 C21a6~ 6
5 9
The use of O'Neal & Benson's value for k5 and of that of Shepp (I956) for
kg,
with
k11 assumed equal to
kg,
leads to a rate of acetone
production
which is two to three
orders of magnitude lower than that observed.
The alternative proposal that acetone is formed by reaction [8] seems to be con-
sistent with all of the facts. Thus the value of
k8
can be calculated from the data in
two completely different ways, with excellent agreement:
(1) From the rates of formation of acetone and ethane, and using
kg
from Shepp
(I956):
VC03COCH3 -8
[CH300I-3](
vC2H6
k9
whence k8
= 7-1 x 106 ml. mole-1 s-1.
24-2
(2) From the rates of formation of acetone and methane, and using our value
of
k4,
VCH3COCII3
_ k8
f-I TT 4k ~~~~~~~~(8)
whence k8 = 70 x 106 ml. mole-1 s-1.
Hydrogen
production
Trenwith (i 963) reported that hydrogen production showed an induction period,
and that the process was second order in acetaldehyde. In the present study
no induction period was found, and the order of hydrogen production was 1P4,
as shown by the double logarithmic plot in figure 4. If the simple Rice-Herzfeld
mechanism were valid the hydrogen production would be a measure of the rate of
the initiation process, and this was Trenwith's conclusion. In terms of the mechan-
ism proposed, however, hydrogen can result from reactions [3], [7] and [8], and
the rate of its formation is not simply related to the rate of initiation.
2
-
bH 4
-
+
1 2 3 0 10 20 30
log1o (P mmHg) 104 [CH3CHO]l (molei ml.-i)
FIGURE 4. Plot of
log1o
vH2 against FIGURE 5. Plot of vH2/[CHI3CHO] against
log10 P (mmHg); T = 523 ?C. rCH3CHOI! at 523 OC.
Application of the steady state treatment leads to the following expression for
the rate of hydrogen production:
=H2
kj[CH3CHO]
+ (k6 + k8)
(kcl/kg)
[CH3CHIO]& (9)
According to this, a plot of
vH1/[CIH3CHO]
against [CH3CHlO] should be linear;
figure 5 shows that this is the case, and from the intercept on the ordinate it is
concluded that k1 at 523?C is 5 0 x 10-7s-1. This is somewhat higher than the
value of 2-5 x 10-7 S-1 obtained from the overall rate; it is difficult at the present
stage to say which value is the more reliable.
The slope of the plot in figure 5, together with the values of k1 and
kg,
allows
k6 + k8 to be obtained: the value is 8 8 x 106 ml. mole-1 s-1. From the rate of acetone
production we deduced that k8 is 7 0 x 106 ml. mole-1 s-1, so that it follows that k6 is
1.8 x 106 ml. mole-' s-1. It is to be noted that k6/k4 is 2 1 x 10-4. This estimate of k6 is
considered to be less reliable than the one made in a later section, but the dis-
crepancy is not great.
Propionaldehyde production
The fact that propionaldehyde is formed as an initial product suggests the pre-
sence of the radical CH2CHO, which is presumably formed by reaction [6]. The
participation of this radical was previously suggested by Wall & Moore
(I95I)
to account for the mixed products formed in the pyrolysis of a mixture of CH3CHO
and CD3CD0.
Because propionaldehyde decomposes rapidly at the temperatures of these
experiments (Eusuf & Laidler I965) it is difficult to make a reliable estimate of
its initial rate of formation; the rate is similar to, but smaller than, the rate of
ethane production (cf. table 1). At a pressure of 117 mmHg, the rate of propionalde-
hyde formation is estimated to be 1-5 x 10-13 mole ml.- s-1, as compared with a
rate of 59 x 10-13 mole ml.-1 s-1 for the rate of ethane production.
Besides undergoing reactions [7] and [10], the CH2CHO radical might undergo
the isomerization reaction
[12]
CH2CHO
+ CH3CHO
1
CH3CHO +
CH3CO.
Since, however, the CH2CHO radical will be considerably stabilized by resonance
this reaction will not be very important; if its activation energy is greater than
10kcal/mole it will be much less important than [7] under the conditions of the
present work.
Ketene production
Ketene decomposes rapidly under the conditions of the present experimelnts,
so that it was not possible to make a direct measurement of its rate of formation.
This rate can, however, be estimated on the basis of a material-balance equation
V12
=
VCH3COCH3
+
VC2HG
+
VC2H,CHO
+
VCH2CO, (10)
which is readily derived from the steady state equations. At an initial acetaldehyde
pressure of 117 mmHg the rate of ketene formation is found to be, from the rates
in table 1,
VCH2CO=
266 x 10-13 mole
m1-1
s-1.
The steady state equation for the radical CH2CHO is
V6
V7+V10
=
VCH,CO+VC2H5CHO,
(11)
so that, at 117 mmHg, v
28.1
x
10-13mole
ml.-1
s-1.
The ratio of the rates of reactions [6] and [4] is therefore
v6_28*1 xl 101
_ ________ = 8&6 x 10 w'
V4
32*6 x 10-10
This is the ratio of the rate constants and it follows that k6
=
7-5 x 106. If the fre-
quency factors of reactions [4] and [6] are the same the activation energy of [6]
is 11 2keal/mole higher than that of [4], or is 18-7kcal/mole. This difference in
activation energies is of interest in view of the fact that D(H-CH2CHO) is probably
about 102 keal/mole, which is 15 kcal/mole greater than D(CH3C0-H) (Benson
I965).
The relative concentrations of [CH2CHO] and [CH3] can be estimated from the
relations VC2H5CHO
k1o[CH31] [CH2CH0]
(12)
and
VC2H6
=
kg[CH3]2.
(13)
It follows that
[0H20H0] k9VCHCH(
[CH3CHO
k10VC:2H6
(14)
If
k9
and
k1o
are equal
[CH2CH0]
= 15 x 1013
[0113] -5*9 x 10 0-025.
(15)
It was noted above that
[CH3C01/[CH31
is 10-2 to 10-3. Although formed much less
rapidly CH2CHO is present in much higher concentrations than CH3C0, because
of its lower reactivity.
Other minor products
The earlier work (Trenwith I963) appeared to indicate that ethylene was a
primary product of the reaction. The present results show a much lower rate of
ethylene production with no detectable induction period. This result is consistent
with the conclusion that the ketene formed in reaction [7] breaks down very rapidly
at these temperatures (Guenther & Walters
I959).
The rate of carbon dioxide production is initially low or zero, but increases and
finally decreases. The results are consistent with the hypothesis that the carbon
dioxide is formed from ketene, which according to Guenther & Walters
(I959)
rapidly decomposes into two sets of products:
2CH2C00 0C3H4 + C02,
2CH2C0
=
C2H4 + 2C0.
The rate of the first process is, at this temperature, about 5 times that of the second.
No other process in the present system seems likely to produce carbon dioxide.
CONCLIUSIONS
The scheme of reactions proposed for the acetaldehyde pyrolysis appears to give
a satisfactory explanation of the results, in that the rate constants deduced on the
basis of the rates of formation of products are self-consistent and in good agreement
with directly observed values when these are available. Table 2 summarizes the rate
constants determined from the present and from other investigations.
TABLE 2. SUMMARY OF RATE CONSTANTS FOR ELEMENTARY REACTIONS,
OBTAINED IN THIS AND OTHER WORK
k (523 ?C)
(s-1 or ml. mole-' s-1)
present other
reaction work values reference
[1] CH3CHO
--
CH3 +CHO 2-5 x 10-7 1P5 x 10-7 Benson
(I960)
[4] CH3 + CH3CHO
-+
CH4 + CH3CO
8 6 x 109 8 7 x 109 Brinton & Volman
(1952)
4*4 x 109 Kerr & Calvert (I965)
[5]
CH3CO CH3
+CO
1- 6 x 106
(ko)
O'Neal & Benson
(i
962)
CH3CO-+CH3+CO - ~~~~~1 6x IO" (k0)J
[6] CH3 + CH3CHO CH4 + CH2CHO
7*5 x 106
[8] CH3 + CH3CHO CH3COCH3 +
H 7*0 x 106 -
[9] CH3 + CH3
--
C2H6 2-2 x 1013
Shepp (1956)
The authors are indebted to the National Research Council of Canada and the
Petroleum Research Fund (administered by the American Chemical Society)
for grants in support of this work. They thank Dr Margaret H. Back for valuable
discussions and assistance, Dr R. R. Fraser for nuclear magnetic resonance analyses
and Dr J. L. Holmes for mass spectrometric analyses. Thanks are also due to Dr
A. B. Trenwith for valuable comments.
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The Mechanism of The Acetaldehyde Pyrolysis

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The Mechanism of the Acetaldehyde Pyrolysis

Author(s): K. J. Laidler and M. T. H. Liu

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