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DE LA FACULTAD DE INGENIERÍA
REVIST
A TÉCNICAREVISTA TÉCNICA
“Buscar la verdad y aanzar
los valores transcendentales”,
misión de las universidades en
su artículo primero, inspirado
en los principios humanísticos.
Ley de Universidades 8 de
septiembre de 1970.
“Buscar la verdad y aanzar
los valores transcendentales”,
misión de las universidades en
su artículo primero, inspirado
en los principios humanísticos.
Ley de Universidades 8 de
septiembre de 1970.
VOLUME 43
SEPTEMBER - DECEMBER 2020
NUMBER 3
Rev. Téc. Ing. Univ. Zulia. Vol. 43, No. 3, 2020, September-December, pp. 114 - 176
Gas-Phase Thermolysis of Ethyl Chlorooxoacetate:
Comparison with Ethyl Oxoacetate and Static System Details
for Kinetic Study
Andreína Alexandra Reyes Yanes
Universidad Nacional Mayor de San Marcos, Facultad de Química e Ingeniería Química, Departamento
Académico de Fisicoquímica. Ciudad Universitaria- Pabellón B- Calle Germán Amezaga Nº 375- Lima- Perú
15081. areyesy@unmsm.edu.pe
https://doi.org/10.22209/rt.v43n3a01
Received: 03/03/2020 | Accepted: 05/06/2020 | Available: 01/09/2020
Abstract
catalysts or solvents that interact with the substrate. So far, gas phase thermolysis of esters derived from oxalic acid have
been scarcely studied. In this investigation, the kinetic study of the thermal decomposition of ethyl chlorooxoacetate between
543–593 K and 76–209 mbar was carried out, using a static vacuum system whose operation are widely described. Total
and homogeneous for substrate decarbonylation, followed by ethylene elimination, unlike the ethyl oxoacetate thermolysis,
which proceeds by parallel decarboxylation and decarbonylation pathways. Arrhenius equation for the reaction studied
between 543.2 – 593.1 K was found to be log k
1
= (13.22 ± 0.45)– (179.4 ± 4.9) kJ mol
–1
(2.303RT)
–1
greater tendency than hydrogen to migrate to the adjacent carbonyl, forming more rigid bonds transition state.
Keywords: thermolysis; gas-phase kinetics; decarbonilation
Termólisis de Clorooxoacetato de Etilo en Fase Gas:
Comparación con Oxoacetato de Etilo y Detalles del Sistema
Estático para el Estudio Cinético
Resumen
catalizadores ni disolventes que interactúen con el sustrato. La termólisis en fase gas de los ésteres derivados del ácido
oxálico ha sido poco estudiada. En esta investigación se realizó el estudio cinético de la descomposición térmica de
clorooxoacetato de etilo entre 543–593 K y 76–209 mbar, utilizando un sistema estático de vacío cuyo funcionamiento se
de orden uno, unimoleculares y homogéneas, de decarbonilación del sustrato seguida de la eliminación de etileno, a
diferencia de la termólisis de oxoacetato de etilo, que procede por vías paralelas de decarboxilación y decarbonilación. La
ecuación de Arrhenius para la reacción estudiada entre 543,2 – 593,1 K resultó ser log k
1
= (13,22 ± 0,45)–(179,4 ± 4,9) kJ
mol
–1
(2,303RT)
–1
de etilo sugiere que el sustituyente cloro tendría mayor disposición que el hidrógeno de migrar al carbonilo adyacente,
formando un estado de transición con enlaces más rígidos.
Palabras clave: termólisis; cinética en fase gas; clorooxoacetato de etilo
Rev. Téc. Ing. Univ. Zulia. Vol. 43, No. 3, 2020, 114-121
Rev. Téc. Ing. Univ. Zulia. Vol. 43, No. 3, 2020, September-December, pp. 114 - 176
115
Thermolysis of EthylChlorooxoacetate
Introduction
Homogeneous reactions can take place in the gas
and solution phase. In the latter, there is a high probability
that solvents, like surfaces and catalyst, may interact
reason, gas-phase reactions do not constrain the use of
quantum mechanical models for estimating the kinetic
parameters and for studying the behavior of the isolated
molecule in the transition state. However, even though
gas-phase thermolysis are important for being a rare case
of order one reactions and, additionally, for clarifying the
structure-reactivity relationship on certain substrates
under study [1-9], the number of elementary gas-phase
reactions is relatively small [10]. Oxalic acid analogs have
been scarcely investigated in gas phase. A theoretical-
experimental study on methyl chlorooxoacetate [11]
suggests the following mechanism, sustained by the
agreement of the values calculated by semi-empirical
methods PM3 and ab initio MP2/6-31G* with the
experimental results at 573 K:
Figure 1. Methyl chlorooxoacetate thermolysis at 573 K.
The static method implies a closed reactor
system to measure the total pressure of the gas generated
as the reaction advances at constant volume, combined
with the chemical analysis of the products at working
temperature. In light of these considerations, this study
aims at describing the static system for estimating
the kinetic and thermodynamic parameters of ethyl
chlorooxoacetate thermolysis in order to suggest a
mechanism for this reaction and to make a comparison
with what has been reported on ethyl oxoacetate [12],
another ester derivative of oxalic acid.
Experimental
Vacuum line. It is manufactured with Pyrex
glass and contains a Pyrex glass cylindrical reactor (Figure
2). The reactor remains inside an oven with controlled
temperature and attached to the manometer and to the
glass membrane that is responsive to changes in pressure.
The products are collected in Pyrex-glass traps at liquid
nitrogen temperature. The system is coupled with a
rate of 50 L min
–1
, that generates a vacuum of 6.67x10
–4
mbar. It also includes a mercury diffusion pump of 150 W
in order to provide additional vacuum.
Figure 2. Static vacuum system. 1, oven. 2, reactor. 3,
glass membrane. 4, relief valve. 5, digital multimeter.
2
,
propylene and ethylene containers, respectively. 11,
temperature controller. 12, vacuum pump. 13, trap for
collecting gas product. 14, mercury diffusion pump. 15,
rubber hose. 16, trap for collecting product for analysis.
Glass membrane.
of 0.5 thick, coated with a thin layer of aluminum, inserted
in the diaphragm and connected by a capillary tube to
the reactor at its lower end and to the manometer at its
upper end (Figure 3). It is lit by a lamp that produces
equilibrium point before the reaction starts. This relative
zero corresponds to pressure equality on both sides of the
membrane. An increase of pressure in the system due to
thermolysis causes membrane deformation and sets in
motion the indicator line with respect to the equilibrium
point. This is measured by introducing air at the upper
end of the membrane with the help of the relief valve until
the indicator line is back to the reference position, and
thus the manometric height reached is equivalent to the
reactor total internal pressure.
Figure 3. Optical system. 1, manometer connection. 2,
glass membrane. 3, capillary tube. 4, reactor stopcock. 5,
lamp. 6, display with indicator line: a, in equilibrium; b,
with an increase in the reactor pressure; c, in vacuum.
Rev. Téc. Ing. Univ. Zulia. Vol. 43, No. 3, 2020, September-December, pp. 114 - 176
116
Reyes Yanes
Oven with temperature controller. It contains
the reactor and is covered by a heating jacket of 200 V and
temperature variation is ± 0.2 K and it stays constant
thanks to an OMEGA SSR240AC45 controller, coupled
to an iron-constantan thermocouple and inserted into a
whole inside the metallic block. The working temperature
is measured with an iron-constantan thermocouple
connected to the digital multimeter.
Figure 4. Longitudinal Cross section of the oven.
1, metallic block. 2, reactor. 3, thermocouple. 4,
injection point with a silicone cap. 5, capillary tube. 6,
thermocouple.
Calculation of kinetic data
The measures were carried out within a range of
543–593 K and 76–209 mbar. After creating a vacuum in
the system, the stopcock is closed to isolate the reactor.
Approximately 0.20 mL of substrate were injected to the
reactor with a PERFEKTUM® syringe through the silicone
cap. The pressure increment generated by gaseous
products in the reactor is measured at appropriate time
intervals. The substrate initial pressure in the reactor
P0 is determined by extrapolation to zero time of a total
pressure curve as a function of time. When additives, such
as free inhibitors and standard radicals, are required, they
and the substrate is injected next. Products undertake a
gas or liquid phase chromatographic analysis at room
temperature, depending of their physical state. When
the necessary extent of reaction is reached, products are
extracted from the reaction camera and condensed using
liquid nitrogen in the PYREX glass traps connected to
the vacuum system, from which air has been previously
extracted. Once room temperature is reached, each sample
is injected to the chromatograph until reproducible results
are obtained.
Substrate characterization
Organics, CAS Nº 4755-77-5), which was 98% pure, was
Reaction products characterization
Gas-phase chromatographic analysis. The
chromatograph coupled with a VARIAN 4400 integrator
with a detector FID (15 mL min
–1
H
2
and 120 mL min
–1
air)
and a column packed with PORAPAK Q 80/100 mesh (3.1
m long), with N
2
(30 mL min
–1
) and propylene (Matheson,
Gas Products, Inc.) as carrier gas and internal standard,
respectively. The oven temperature was 373 K, and the
equation obtained from the calibration curve was the
following:
Liquid-phase chromatographic analysis.
Ethyl chloroformate, main thermolysis product observed,
was analyzed with a HEWLETT- PACKARD 5710-A
chromatograph coupled with HP 3392-A integrator and
equipped with detector FID (30 mL min
–1
H
2
and 240
mL min
–1
air), with column packed with 10% SP 1200,
1% H
3
PO
4
, Chrom WAW 80/100 mesh (2 m long), the
oven temperature being 313 K, with N
2
as carrier gas (30
mL min
–1
) and acetone p.a. (Merck, CAS Nº 67-64-1) as
internal standard. The following equation was obtained
from calibration curve:
Ethylene, CO
2
and ClCOOC
2
H
5
among the reaction products, which suggests that they
could be involved in the following reaction routes:
Figure 5. Possible thermal decomposition routes for
ethyl chlorooxoacetate.
2
H
5
thermolysis [13] results from the following equation for
559 - 626 K:
of all the reactions shown in Figure 5 in the working
temperature range (543–593 K) is to determine the
(1)
(2)
(3)
Rev. Téc. Ing. Univ. Zulia. Vol. 43, No. 3, 2020, September-December, pp. 114 - 176
117
Thermolysis of EthylChlorooxoacetate
pressure of the ethylene produced and then compare it to
the one calculated for the hypothetical reaction 3. If they are
equal, only one route occurs: substrate decarbonylation,
1, whose reaction intermediary generates ethylene upon
decomposition. If the calculated ethylene pressure by
chromatographic analysis is higher than the one of the
ethylene resulting from ClCOOC
2
H
5
pyrolysis, it means that
two parallel reactions are taking place and the remaining
ethylene was generated from decarboxylation, 2. The
following expression allows to determine the pressure
of ethylene produced by ClCOOC
2
H
5
pyrolysis at any
time t, being residual ClCOOC
2
H
5
pressure obtained from
equation (2).
Results and Discussion
Stoichiometry. The products shown in Figure 5
were found throughout the working temperature range.
it was detected with a high-voltage generator [12]. Table
1 shows a comparison of theoretical results obtained
from equation (4) for the expected pressure of ethylene
from ClCOOC
2
H
5
thermolysis, with the actual ethylene
pressure obtained from equation (1). The difference
between these values at the respective reaction times for
originates from ClCOOC
2
H
5
decomposition and a parallel
decarboxylation reaction does not occur as in ethyl
oxoacetate thermolysis.
Table 1. Comparison between total ethylene analyzed
in ethyl chlorooxoacetate thermolysis and ethylene
generated by ethyl chloroformate thermolysis at different
temperatures.
T (K)
Parameter Value
563.2
t (min)
20 30 40
P
ethylene, GC
(mbar)
0.19 0.29 0.27
P
ethylene generated from ClCOOEt
(mbar)
2.00 2.93 3.60
573.2
t (min)
12 15 20
P
ethylene, GC
(mbar)
2.53 3.07 3.73
P
ethylene generated from ClCOOEt
(mbar)
2.40 2.93 3.87
593.1
t (min)
2 3 6
P
ethylene, GC
(mbar)
0.67 1.47 3.73
P
ethylene generated from ClCOOEt
(mbar)
0.80 1.60 4.00
The produced ethylene pressure is low because
ClCOOC
2
H
5
thermolysis in the working range is very slow.
On the other hand, even though the HCl analysis was
not carried out, it was possible to detect the presence of
CO in the vacuum line. Based on these observations, the
following sequence of reactions for ethyl chlorooxoacetate
thermal decomposition may be suggested:
Figure 6.
pyrolysis.
The similarity of reaction percentage yield
determined through the different methods is evident in
Table 2, which supports the stoichiometry proposed. For
each reaction time, they were obtained from the following
equations, where P
0
is substrate initial pressure within the
reactor:
Table 2.
chlorooxoacetate thermolysis at 573.2 K.
Parameter Value
t (min)
7 10 12 15 20
Reaction percent yield
(chromatographic method)
26.2 33.5 41.0 46.8 54.8
Reaction percent yield
(manometric method)
26.9 34.6 40.4 46.8 56.4
Reaction order. The linear correlation shown
decarbonylation reaction in ethyl oxoacetate thermolysis.
Figure 7. First-order graph for ethyl chlorooxoacetate
thermolysis.
(4)
(5)
(6)
Rev. Téc. Ing. Univ. Zulia. Vol. 43, No. 3, 2020, September-December, pp. 114 - 176
118
Reyes Yanes
from the following equation:
]/)log[()/303,2(
0ClCOOEt01
PPPtk −−=
Inhibitor effect. In order to prevent the reaction
from following a free radical chain mechanism [14-18],
instead of using the molecular route, toluene was utilized
as radical inhibitor [20-25] in different proportions. It
can be observed in Table 3 how the invariability of the
indicates that the reaction under study was not inhibited,
which suggests a molecular mechanism.
Table 3.
in ethyl chlorooxoacetate thermolysis at 582.5 K.
Inhibitor
pressure,
P
i
(mbar)
Initial
pressure,
P
0
(mbar)
Relation
P
i
/P
0
10
4
k
1
(s
–1
)
Average
<10
4
k
1
>
(s
–1
)
DSR
(%)
111.99 – 7.10
6.99 ±
0.09
1.29
119.99 98.66 1.22 6.97
183.32 93.33 1.96 6.88
258.65 83.99 3.08 6.99
Homogeneity. In order to verify that thermolysis
occurred quantitatively in gas phase [26-28], it was
additionally carried out in a reactor internally packed
with small Pyrex glass cylinders with a surface-area-to-
volume ratio of 6.22 cm
–1
(Figure 8), assuming a 1:1 ratio
consistent when both reactors were internally covered
with a layer of the carbon produced in allyl bromide
thermolysis at above 673 K [29]. It was not possible to
obtain reproducible results in reactors with no carbon
coating, which reveals that the nature of the glass surface
Figure 8. Packed Pyrex glass reactor: 1, clean. 2, coated
with carbon in thermolysis at 673 K after injecting allyl
bromide.
under such conditions.
Table 4. Homogeneity in ethyl chlorooxoacetate thermal
decomposition at 573.2 K.
10
4
k
1
(s
–1
)
Unpacked reactor
(SA:V = 1 cm
–1
)
Packed reactor
(SA:V = 6.22 cm
–1
)
7.05 ± 0.16 7.70 ± 0.38
Temperature Effect
The kinetic parameters were determined by
linear regression of the results in Table 5 and Figure 9,
which also corresponds to Arrhenius plot.
Table 5. Arrhenius plot values for ethyl chlorooxoacetate
thermolysis.
T (K)
543.2 552.9 563.2 573.2 583.3 593.1
10
4
k
1
(s
–1
)
1.01 1.80 3.82 7.00 13.47 29.36
Figure 9.
(9371.9 ± 256.0) K. Intercept: (13.22 ± 0.45). R
2
= 0.9990
Thus, the Arrhenius equation was obtained for
the reaction between 543.2 – 593.1 K:
Based on the transition state theory, it is possible
to determine the kinetic and activation thermodynamic
parameters, through the following equations for
unimolecular reactions:
(7)
(8)
(9)
(10)
Rev. Téc. Ing. Univ. Zulia. Vol. 43, No. 3, 2020, September-December, pp. 114 - 176
119
Thermolysis of EthylChlorooxoacetate
The results obtained by extrapolation at 623 K
are presented in Table 6. This temperature was chosen
to be able to include the results of ethyl oxoacetate
decarbonylation, in order to discuss the effect of the
substituent to carbonyl group on reactivity.
Table 6. Comparison between the kinetic parameters
obtained at 623 K in the ethyl oxoacetate decarbonylation
and ethyl chlorooxoacetate reactions.
Z
a
10
4
k
1
(s
–1
)
log A
E
a
(kJ mol
–1
)
ΔH≠
(kJ
mol
–1
)
ΔS≠
(J
mol
–
1
K
–1
)
ΔG≠
(kJ
mol
–1
)
Ref.
Cl 151.57
13.22 ± 0.45 179.4 ± 4.9
227.7 – 6.3 178.1
b
H 0.034
14.06 ± 0.54 232.9 ± 7.0
174.2 9.8 22.6 9
a
Substituent in the acylic part of the ester
b
This study
In light of these results, a mechanism involving
decarbonylation and ethylene elimination is suggested. In
this case, consecutive reactions occur, in contrast to ethyl
oxoacetate thermolysis, in which parallel reactions take
place.
Figure 10. Mecanism for ethyl chlorooxoacetate thermal
decomposition.
In both cases, positive values of enthalpy and
activation free energy suggest endothermic and endergonic
transition states. The negative value of activation
entropy in ethyl chlorooxoacetate decarboxylation can
be attributed to the formation of a triple bond in the
transition state, which decreases the degrees of freedom.
This contrasts with the ethyl oxoacetate decarbonylation
reaction, whose positive activation entropy can be due
to the fact that the acylic hydrogen may form less rigid
bonds in the transition state given its acid/nucleophile
dual behavior. The chlorine substituent seems to assist the
decarbonylation reaction over the elimination reaction.
This behavior can be explained in terms of electronic
transmission: the chlorine atom is a good “leaving” atom
and has non-bonding electronic pairs. These properties
allow it to migrate and attack nucleophilically the positive
(11)
charge density generated in the carbon atom of its
neighbor carbonyl group in transition state. This behavior
suggests that the more electronegative the substituent is,
the higher its tendency to migrate to its neighbor carbonyl
will be, since it tends to attract the electronic density of
its neighbor carbonyl as the bond of the adjacent carbonyl
groups is weakened in transition state, as shown in Figure
of ethyl chlorooxoacetate decarbonylation is dramatically
higher than in ethyl oxoacetate.
Conclusions
In view of the qualitative-quantitative analysis of
products and kinetic parameters obtained, it is possible to
propose a decarbonylation mechanism, with consecutive
decarboxylation and ethylene elimination reactions, for
the unimolecular and homogeneous elimination of ethyl
chlorooxoacetate. Ethyl chlorooxoacetate activation
entropy is negative because chlorine has a salient tendency
to migrate to its neighbour carbonyle, forming bonds
with fewer degrees of freedom in the transition state.
The tendency displayed by a substituent to migrate to
the adjacent carbonyl group in decarbonylation reactions
seems to be directly proportional to its electronegativity.
At the same temperature, the ethyl chlorooxoacetate
decarbonylation reaction was superior to ethyl oxoacetate
decarbonylation over three magnitude orders.
Acknowledgement
I would like to express my gratitude to the
especially to the team at the Physical Organic Chemistry
Laboratory.
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