Thermal decomposition of cyclic organic peroxides in pure solvents and binary solvent mixtures

Article abstract of DOI:10.1002/kin.20487

The thermal decomposition reaction of acetone cyclic triperoxide, acetone cyclic diperoxide, 4-heptanone cyclic diperoxide, and pinacolone cyclic diperoxide ca. 0.02 M was studied in pure solvents (acetone and 1 -propanol) and in binary mixtures of acetone/1-propanol at 150°C. The kinetics of each system was explored by gas chromatography (GC) at different solvent compositions. The reactions showed a behavior accordingly with a pseudo-first-order kinetic law up to at least 90% peroxide decomposition. The main organic products derived from these thermolysis reactions were detected by GC analysis. Among them, the corresponding ketones, methane, ethane, and propane were the main identified products. The rates of decomposition of pinacolone diperoxide in the pure solvents were practically independent of the solvent characteristics, so it was of no interest to analyze its kinetic behavior in binary solvent mixtures. In acetone/1-propanol mixtures, the solvation effect on the cyclic peroxides derived from 4-heptanone and acetone molecules was slightly dominated by specific interactions between 1-propanol and a diradical-activated complex initially formed. This species was preferentially solvated by 1-propanol instead of acetone. Specific interactions between the O atoms from the peroxidic bond and the H from the OH in 1-propanol can be taken into account.

Full text of DOI:10.1002/kin.20487

Thermal Decomposition of
Cyclic Organic Peroxides in
Pure Solvents and Binary
Solvent Mixtures
´
´
˜
MARIANGELES IGLESIAS, GASTON P. BARRETO, GLADYS N. EYLER, ADRIANA I. CANIZO
Facultad de Ingenier´ıa, Universidad Nacional del Centro de la Provincia de Buenos Aires. Avenida del Valle 5737, B7400JWI,
Olavarr´ıa, Buenos Aires, Argentina
Received 25 August 2009; revised 23 December 2009; accepted 17 January 2010
DOI 10.1002/kin.20487
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: The thermal decomposition reaction of acetone cyclic triperoxide, acetone cyclic
diperoxide, 4-heptanone cyclic diperoxide, and pinacolone cyclic diperoxide ca. 0.02 M was
studied in pure solvents (acetone and 1-propanol) and in binary mixtures of acetone/1-propanol
at 150◦C. The kinetics of each system was explored by gas chromatography (GC) at different
solvent compositions. The reactions showed a behavior accordingly with a pseudo-first-order
kinetic law up to at least 90% peroxide decomposition. The main organic products derived
from these thermolysis reactions were detected by GC analysis. Among them, the correspond-
ing ketones, methane, ethane, and propane were the main identified products. The rates of
decomposition of pinacolone diperoxide in the pure solvents were practically independent of
the solvent characteristics, so it was of no interest to analyze its kinetic behavior in binary
solvent mixtures. In acetone/1-propanol mixtures, the solvation effect on the cyclic peroxides
derived from 4-heptanone and acetone molecules was slightly dominated by specific inter-
actions between 1-propanol and a diradical-activated complex initially formed. This species
was preferentially solvated by 1-propanol instead of acetone. Specific interactions between
the O atoms from the peroxidic bond and the H from the OH in 1-propanol can be taken into
account. ꢀ 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 347–353, 2010
C
toluene and acetone/1-propanol mixtures has been re-
cently reported [1]. The mixed solvents chosen were
representative of the types for mixtures of aprotic
nonpolar/aprotic mildly polar (toluene/acetone) and
protic/aprotic (1-propanol/acetone) solvents. The last
of these mixtures has been considered as a syner-
getic binary solvent system [2], where the interac-
tion through hydrogen bonds between the solvents
generates a complex with a solvent polarity index
value [ET (30)] [3] higher than those of the two
pure solvents. In that complex, acetone operates as
INTRODUCTION
A kinetic study of the solvent influence on the ther-
mal decomposition reaction of diethylketone cyclic
triperoxide (1b in Scheme 1) at 150◦C in acetone/
Correspondence to: Adriana I. Can˜izo; e-mail: acanizo@fio
.unicen.edu.ar.
Contract grant sponsor: Universidad Nacional del Centro de la
Provincia de Buenos Aires (UNCPBA).
c
ꢀ
2010 Wiley Periodicals, Inc.

348
IGLESIAS ET AL.
tigated and discussed in terms of preferential solvation.
A reaction mechanism to interpret the formation of the
different reaction products is proposed.
EXPERIMENTAL
Materials
Cyclic peroxides 1a (mp 96–97◦C) [5], 2a (mp
132–133◦C) [6], 2b (mp 47–48◦C) [7], and 2c (mp
124◦C) [8] were synthesized, purified, and char-
acterized in accordance with techniques described
in the literature. Acetone (Merck, Buenos Aires,
Argentina; analytical grade) was purified follow-
ing methods described elsewhere [9] (bp 56◦C).
1-Propanol (Mallinckrodt, Hobart, NY, USA; ana-
lytical grade) was distilled from ethylendiaminote-
traacetic acid disodium salt dihydrate to remove traces
of metallic ions (bp 97◦C) [10]. Sublimed naphtha-
lene (Mallinckrodt; A.R.) was employed as an internal
standard in quantitative GC determinations.
Scheme 1 1a, R1 = R2 = CH3 (ACTP); 1b, R1 = R2 =
CH2CH3 (DEKTP); 1c, R1 = R2 = –(CH2)5–(CHTP).
a dipolar hydrogen-bond acceptor and 1-propanol as a
hydrogen-bond donor.
It has long been recognized that the reactivity of
some cyclic organic diperoxides and triperoxides in
different solvents is notably affected by the solvent po-
larity. Most of the analyses of solvent effects have been
performed in pure solvents showing how extensive and
complex the interactions of the substrate and/or the in-
termediate(s) with the solvent molecules may be [4].
In this work, an extensive analysis of the thermal
decomposition reactions of acetone cyclic triperox-
ide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxacy-
clononane, 1a), acetone cyclic diperoxide (3,3,
Kinetic Methods
Pure solvents were mixed by volume to give binary
solvent mixtures of different mole fraction composi-
tions. Solutions of cyclic peroxide were about 0.02 M
with 0.2% (M/V) naphthalene added as an internal
standard to perform quantitative analyses by gas chro-
matography (GC). An appropriate solution of perox-
ide in acetone/1-propanol mixtures was placed in a
Pyrex glass ampoule (10 cm long × 4 mm OD), thor-
oughly degassed under vacuum at −196◦C and then
sealed with a flame torch. These ampoules were im-
mersed in a thermostated silicone oil bath ( 0.1◦C) at
150◦C. After predetermined times, the reaction in the
ampoule was stopped by cooling at 0˚C in an ice-water
bath. The concentrations of cyclic peroxide remain-
ing in the solution were determined by GC analysis
(internal standard method) in a Rtx-5MS capillary col-
umn (5% biphenyl–95% dimethyl polysiloxane, 30 m,
0.25 mm ID, 0.25 μm film thickness), installed in a
Thermo Quest Trace 2000 GC model gas chromato-
graph with helium as a carrier gas (0.5 mL min−1),
FID detection (250◦C), and injection port at 150◦C in
split mode (split ratio: 1:33, split flow: 33 mL/min).
The experiments were carried out under programmed
conditions (60◦C, 5 min, 10◦C/min, 250◦C, 1 min).
Retention times of cyclic peroxides were ca. 6 min for
2a, ca. 11 min for 1a, ca. 15 min for 2c, and ca. 17 min
for 2b. Under these experimental conditions, the naph-
thalene used as internal standard had a retention time
of 12 min.
6,6-tetramethyl-1,2,4,5-tetraoxacyclohexane,
4-heptanone diperoxide (3,3,6,6-tetra-n-propyl-
1,2,4,5-tetraoxacyclohexane, 2b), and pinacolone
diperoxide (3,6-dimethyl-3,6-di-tert-butyl-1,2,4,5-
2a),
tetraoxacyclohexane, 2c) in pure solvents (acetone
and 1-propanol) and in acetone/1-propanol binary
mixtures is evaluated (Schemes 1 and 2).
The aim of this work is to (a) investigate the solvent
effects on the reactivity of different cyclic peroxides
and (b) study substituent effects on the homolytic O O
rupture.
Some correlations of the kinetic data with the com-
position of the binary solvent mixture have been inves-
Scheme 2 2a, R1 = R2 = CH3 (ACDP); 2b, R1 = R2 =
CH2CH2CH3 (HDP); 2c, R1 = CH3; R2 = (CH3)3 C (PDP).
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THERMAL DECOMPOSITION OF CYCLIC ORGANIC PEROXIDES
349
The corresponding experimental pseudo-first-order
rate constants (kexp in s−1) were calculated with 5%
accuracy from the slope of the straight line obtained
by plotting the values of ln [cyclic peroxide]t vs. reac-
tion time at 150◦C; correlation coefficients (r ≥ 0.997)
were obtained by a conventional least-mean-square
program.
peroxide substituents generate changes in the reaction
rates.
The identification of reaction products was done by
GC analyses by comparing the retention time of each
product, from a sample prepared with the correspond-
ing reagents, with the retention time of that compound
in the reaction mixture. The identification was con-
firmed by co-chromatography. Other products were
identified by GC-MS analysis with a mass selective
detector Finnigan Polaris installed in the Trace 2000
equipment. (Note that cyclic organic peroxides must
be handled with care because they can be detonated by
shock.)
Solvent Effects
RESULTS AND DISCUSSION
Kinetic Determinations
Decomposition of Acetone Triperoxide (1a) in 1-Pro-
panol and Acetone/1-Propanol Mixtures. The ther-
mal decomposition of acetone triperoxide was stud-
ied in 1-propanol and in binary mixtures of acetone/
1-propanol at 150◦C (Table I). The reaction follows a
pseudo-first-order kinetic law up to conversions of 1a
higher than one half-life. The addition of 1-propanol up
to a mole fraction of 0.1 is enough to duplicate the rate
coefficient of the reaction (kprop(0.1)/kacet = 2.2), but an
increase of the alcohol concentration up to x(PrOH) =
0.7 slightly affects the reactivity of the 1a molecule.
This molecule probably interacts more efficiently with
one component of the binary mixture. Mixtures of dif-
ferent 1-propanol content create similar environments
around compound 1a and provide kexp values close to
that obtained in pure alcohol. Once again, the activated
complex of the reaction is preferentially solvated by
1-propanol.
Rate measurements were made on the thermal decom-
position of four different cyclic peroxides 1a, 2a–c
(Schemes 1 and 2). The corresponding pseudo-first-
order rate constant values are shown in Tables I–IV.
The analyses were carried out at 150◦C in pure sol-
vents (acetone and 1-propanol) and in their binary
mixtures prepared at different mole fractions of cosol-
vent, x(PrOH), to vary the composition systematically
(Tables I–IV). The initial concentration of peroxides
in solution was ca. 0.02 M, so that induced decompo-
sition was probably small enough to be neglected. The
different reaction systems studied showed a consistent
behavior with a pseudo-first-order kinetic law up to
at least 50% peroxide decomposition although some
systems were monitored up to conversions higher than
90%.
The rate-determining step of the thermal decompo-
sition reaction of the cyclic peroxides is the biradical
intermediate formation [11] (Eq. (1)). It is very im-
probable that the biradical-activated complex would
be solvated to the same extent as the starting material
since differences in the electronic configuration, and
therefore polarizability, should exist. The differential
solvation of starting material and biradical-activated
complex should lead to a difference in the reaction rate
and subsequently in the activation parameter (e.g., en-
ergy of activation). The solvent cavity requirement for
the activated complex of a radical reaction should cer-
tainly be different (in size and shape) from that of the
reactant. Changes in the reaction solvent or in the cycle
Table I Pseudo-First-Order Rate Constants (kexp) of
the Thermal Decomposition Reaction of Acetone Cyclic
Triperoxide (1a) at 150◦C in 1-Propanol and Acetone/
1-Propanol Binary Mixtures
x(PrOH)
k
exp × 105 (s−1
)
Conversion (%)
0 (acetone)
0.91a
2.05
1.94
1.73
2.50
50
68
57
64
92
0.1
0.3
0.7
1
aRate constant value from [15].
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350
IGLESIAS ET AL.
Table II Pseudo-First-Order Rate Constants (kexp) of
the Decomposition Reaction of Acetone Cyclic
5.5
5
k
Diperoxide (2a) Thermal at 150◦C in Pure Acetone, Pure
1-Propanol, and Acetone/1-Propanol Binary Mixtures
4.5
4
x(PrOH)
k
exp × 105 × (s−1
)
Conversion (%)
3.5
3
0 (acetone)
0.667
1.50
2.83
2.67
68
91
93
91
0.5
0.7
1
2.5
0
0.2
0.4
0.6
0.8
1
X(PrOH)
Figure 1 Correlation between ln kexp for 2b and 1-propanol
mole fraction, x(PrOH), in binary mixtures of acetone/
1-propanol at 150◦C (including the two pure solvents). [Color
figure can be viewed in the online issue, which is available
at www.interscience.wiley.com.]
Decomposition of Acetone Cyclic Diperoxide (2a)
in Pure Solvents and Acetone/1-Propanol Mixtures.
The rate constant values of the thermal decomposi-
tion reaction of 2a in pure solvents such as acetone
and 1-propanol (Table II) show that the reactivity of
this compound increases up to four times in the pure
protic solvent (kprop/kacet = 4). The thermal decom-
position reaction of 2a was progressively accelerated
in acetone/1-propanol mixtures with the increasing
concentration of the alcohol. The reactivity rises up to
a value close to that obtained in the pure alcohol when
the 1-propanol mole fraction in the binary solvent mix-
tures is 0.7. This solvent system was considered as a
synergetic mixture [2] with a normalized ETN (30) pa-
rameter value of 0.621, which is higher than the ETN (30)
values of the pure solvents (ETN = 0.617 and 0.355 for
1-propanol and acetone, respectively).
The trend shown in Fig. 1 is evident, although the dif-
ferences observed in k values showed a zigzag form.
However, the experimental rate constant values in all
binary mixtures analyzed in this work are far from the
k value determined in pure 1-PrOH.
Decomposition of Pinacolone Cyclic Diperoxide (2c)
in Pure Solvents. The rate constant values at 150◦C
of the thermal decomposition reaction of 2c in two
organic solvents with different physicochemical prop-
erties are presented in Table IV. The rate constant value
increases nearly 8% when acetone solvent is replaced
by 1-propanol as the reaction solvent. This difference
in reactivity in pure solvents—at the experimental con-
ditions of this work—is small and close to the experi-
mental errors, in order to justify an extensive study of
this cyclic diperoxide in some binary solvent mixtures.
Thus, a ratio close to the unit is observed between
rate constant values when acetone solvent is replaced
by 1-propanol (kprop/kacet = 1.09). Probably this in-
vestigation would have sense at a lower experimen-
tal temperature or in mixtures toluene/1-PrOH where
(kprop/ktol ≈ 2; Table V), but this is not the objective
of the present work. In a benzene solution (an apolar
hydrocarbon solvent), the rate constant value corre-
sponding to the thermal decomposition reaction of 2c
at 150◦C was 61 × 10−5 s−1 [12] (Table V). So, it is ev-
ident that in nonpolar solvents the reaction takes place
Decomposition of 4-Heptanone Cyclic Diperoxide
(2b) in Pure Solvents and Acetone/1-Propanol Mix-
tures. Thermal decomposition reaction of 2b at 150◦C
was carried out in pure acetone, pure 1-propanol, and
in their binary mixtures (Table III). The kexp values in-
crease in binary mixtures containing 1-propanol up to
the highest value in pure alcohol (kprop/kacet = 3.23). It
was found that the rate constants increase ca. 1.3 times
in the mixture with x(PrOH) = 0.1 up to at least
1.9 times in the mixture with x(PrOH) = 0.9 in com-
parison with the kexp value obtained in pure acetone.
Table III Pseudo-First Order Rate Coefficient Values
(kexp) of 4-Heptanone Cyclic Diperoxide (2b) Thermal
Decomposition Reaction at 150◦C in Acetone/
1-Propanol Binary Mixtures
x(PrOH)
k
exp × 105 (s−1
)
Conversion (%)
Table IV Pseudo-First-Order Rate Constants (kexp) of
the Thermal Decomposition Reaction of Pinacolone
Diperoxide (2c) at 150◦C in Pure Solvents
0 (acetone)
18.3
24.3
25.7
32.5
26.7
32.2
59.1
89
83
76
56
60
77
87
0.1
0.3
0.5
0.7
0.9
1
Solvent
k
exp × 105 (s−1
)
Conversion (%)
Acetone
1-Propanol
117.8
128.3
98
74
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THERMAL DECOMPOSITION OF CYCLIC ORGANIC PEROXIDES
351
Table V Pseudo-First-Order Rate Constants (kexp) of
the Thermal Decomposition Reaction in Solution of
Some Di- and Triperoxides at 150◦C
reaction solvents in the mixtures, it was not possible to
differentiate it from the reaction product derived from
1a or 2a in the corresponding chromatograms. Thus,
only in pure 1-propanol as solvent, acetone was iden-
tified as an organic product derived form 1a and 2a
thermolysis.
Solvent
Acetone
1a
1ba 1cb
2a
2b
2c
0.91 25.5 57 0.667 18.3 118
Acetone/1-PrOH) 1.73 26.7
–
–
2.83 26.7
2.67 59
–
As consequence of the O O bond fission rep-
resented in Eq. (3), new highly instable biradicals
were formed. Later, decomposition of these through
C C bond ruptures generated different free radicals
(Eq. (4)) capable of to participate in radical–radical
reactions (Eqs. (5) and (6)) or in hydrogen-atom ab-
straction reaction (Eq. (7)). R• (Eq. (5)), represents
the methyl radical from 1a, 2a, or 2c, the n-propyl
radical from 2b, or the stable tert-butyl radical from
2c. Some products detected confirm the existence
of radical–radical coupling reactions (e.g., 2,2,3,3-
tetramethylbutane from 2c and ethane from 1a and
2a). The esters identified (n-propyl butanoate from 2b
and tert-butyl acetate from 2c) are interpreted with the
help of Eq. (6).
x(PrOH) = 0.7
1-Propanol
Toluene
2.5 26.8
128
0.49c 6.60c 14.3 0.28c 5.90c 56.0c
Benzene
–
18.2d 9.55 0.11e
–
61.0e
All values are expressed × 10−5(s−1).
aKinetic data from [1].
bKinetic data from [4c].
cKinetic data at 145◦C from [14].
d Kinetic data from [4a].
eKinetic data from [12].
more slowly than in polar solvent. Some experiments
at 120◦C demonstrated that the reaction can be acceler-
ated ca. four times when the reaction was carried out in
a mixture benzene/2-PrOH—where the mole fraction
of PrOH is ca. 0.6—in comparison with the same re-
action in pure benzene (kbenz = 3.49 × 10−5 s−1 [12],
and kbenz/2−PrOH = 14.8 × 10−5
s
−1 [13]).
Product Analysis. The organic products derived from
thermolysis of the different peroxides in acetone,
1-PrOH, and binary mixtures acetone/1-PrOH may be
interpreted in terms of an initial O O bond homoly-
sis to give an intermediate biradical (Eq. (1)), which
may undergo either C O (Eq. (2)), O O (Eq. (3)), or
subsequent C C (Eq. (4)) bond cleavages.
Radicals derived from cyclic peroxides participate
in hydrogen abstraction reaction with acetone (Eq. (7)),
giving the radical CH3COCH•2. The presence of 2,5-
hexanedione may be justified by a coupling reaction of
these radicals (Eq. (5)). On the other hand, 2-hexanone,
observed as a product of the decomposition of 2b,
can be formed by a radical–radical reaction between
n-propyl radicals and radicals derived from acetone.
Substituent Effects. The variation of the experimental
rate constant by changing the substituent can be clearly
observed when the reactivities of acetone, pinacolone,
and 4-heptanone diperoxides are compared (Tables II–
IV). The presence of methyl groups as substituent of
the tetraoxacyclohexane ring clearly decreases the re-
activity of these compounds, probably because the per-
oxide molecule is highly confined in a solvent cage.
This effect has been detected in previous works while
studying the thermal decomposition reaction of cyclic
peroxides in benzene [12] or toluene [14]. Kinetic data
in these nonpolar solvents are included in Table V. In
The corresponding ketones (acetone, pinacolone, or
4-heptanone) obtained from the diperoxide decompo-
sition may be explained as products derived from C O
fission (Eq. (2)). When acetone was used as one of the
International Journal of Chemical Kinetics DOI 10.1002/kin

352
IGLESIAS ET AL.
both solvents, acetone diperoxide (2a) showed lower
rate constant values than some cyclic peroxides with
bulkier substituents such as n-propyl or tert-butyl. Sol-
vent effect studies of 1a have demonstrated that this
compound is highly stable in solution [15], whereas in
its solid state it shows a very different behavior that
make possible its application as a primary explosive
[16]. However, when the methyl group was replaced by
ethyl (1b in Scheme 1) or the pentamethylene group (1c
in Scheme 1) as substituent on the hexaoxacyclononane
ring, the reactivity was substantially increased
(Table V). It can be observed that, in acetone solvent,
1b [4a] and 1c [4c] decompose 28 and 63 times faster
than 1a, respectively. This trend is also observed in
benzene and toluene solution (Table V).
Conformational studies of 1a [17] and 1b [18]
molecules have demonstrated some differences be-
tween their preferential conformations. 1a shows a
twisted-boat-chair as the lowest energy conformation,
whereas 1b achieves a boat-chair conformation as it
has been found in recent studies of its FTIR spectra
[18]. The environment of the ring carbon atoms in
the 1a molecule would be asymmetric, and this dis-
tortion could be explained by intramolecular repulsion
between the hydrogen atoms of the methyl groups and
the oxygen atoms of the O O bond [17]. Probably, the
differences in reactivity of triperoxides 1a and 1b can
be related to the existence of these differences in their
structural features.
the binary solvent mixture increases by addition of
1-propanol. Analyses of the reaction products confirm
a stepwise mechanism where radical species play an ac-
tive role. On the other hand, pinacolone diperoxide (2c)
with bulky substituent remained unaffected by solvent
changes. Rate constant variations are probably caused
by the presence of the protic solvent, which slightly
dominates the preferential solvation around the cyclic
peroxide molecules. This solvation effect gives account
of the specific interactions between the 1-propanol and
the more polar activated complex represented by the
biradical, initially formed (Eq. (1)). As it has been ob-
served, at x(PrOH) = 0.1 the decomposition reaction
of acetone triperoxide (1a) is accelerated in compar-
ison with that found in pure acetone; but no further
changes in rate constants are observed when increas-
ing the amount of alcohol. These binary solvent mix-
tures with alcohol are considered as synergetic systems
but that effect is not operative in the reactions studied
in the present work. The biradical species is preferen-
tially solvated by 1-propanol instead of by the structure
formed by intersolvent hydrogen-bonded species gen-
erated between molecules of acetone and 1-propanol.
It can be assumed that preferential solvation is an in-
fluencing reactivity factor for the homolytic rupture of
the O O bond of the peroxides studied in this work.
Specific interactions between the O atom in the perox-
idic bond and the H atom in the OH of 1-propanol can
be taken into account.
The experimental rate constant values obtained in
0.7 mol fraction acetone/1-PrOH mixtures (Table V)
demonstrated that only acetone diperoxide shows a
value slightly higher than those obtained in pure sol-
vents. The kexp value in the mixture is nearly 6%
higher than the rate constant value in pure 1-PrOH.
This difference is close to the experimental error and
makes it possible to neglect a preferential solvation of
the 2a molecule by the intersolvent species proposed
by Ortega et al. in 1996 [2]. In general, the peroxide
molecules decompose faster in a mixture containing 1-
PrOH than in pure acetone. A preferential solvation of
these compounds by the alcohol molecule is operative,
but the extent of the effect is affected by substituent
and it is not possible to point out a trend because the
number of peroxides analyzed is not high enough.
AIC is a member of the Carrera del Investigador Cient´ıfico y
Tecnolo´gico, CONICET. GPB is a fellowship holder of the
CONICET.
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International Journal of Chemical Kinetics DOI 10.1002/kin