Thermal Decomposition Reaction of Acetophenone Cyclic Diperoxide in Solvents of Different Physicochemical Properties
Laboratorio de Química, Facultad de Ingeniería, Universidad Nacional del Centro de la Provincia de Buenos Aires, Avda del Valle 5737, (7400) Olavarría, Argentina
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Author to whom correspondence should be addressed.
Molecules 2000, 5(3), 365-366; https://doi.org/10.3390/50300365
Published: 22 March 2000
Abstract
:The thermal decomposition reaction of acetophenone cyclic diperoxide (trans-3,6-dimethyl-3,6-diphenyl-1,2,4,5-tetroxane; APDP) at the initial concentration of c.a. 0.01 mol kg-1 and temperature ranges of 135.5 to 185.0° C has been investigated in dioxane and acetonitrile solutions, and in an 2-propanol/benzene mixture.
Introduction
The aim of this work is to study the thermal decomposition of acetophenone cyclic diperoxide (APDP) in solvents of different physicochemical properties, in order to correlate the kinetic parameters of the reaction and to compare the results with the previous studies in benzene solution [1].
Experimental
The diperoxide was prepared and conveniently purified as described elsewhere [2], and the solvents employed were purified by standar methods [3]. The 2-propanol was destilled from ethylenediaminetetraacetic acid (EDTA) to remove traces of metallic ions.
The diperoxide remaining in the solutions and the reaction products were determined by RP-HPLC.
Results and Discussion
The APDP thermolysis was made in the temperature range of 135,0 - 185,0°C at diperoxide initial concentration c.a. 0.01 molkg-1. The observed rate constant values for APDP thermolysis at 150,0°C in various solvent are shown in Table 1. The reaction follows a first - order kinetic law up to at least c.a. 50% APDP conversion. In this case, the reactivity of the APDP is higher in polar solvent than in no polar-solvent.
The experimental data were statistically treated in order to verify the existence of a true isokinetic relationship and to obtained the value of the isokinetic temperature (β=154,5°C). This value is compared with an other obtained by a different criteria described for kinetic data treatment.
The yields of the reaction products (acetophenone, methane, ethane) supports a stepwise mechanism and make possible to discuss the nature of solvent effects on the reaction.
Acknowledgements
The authors thank the Facultad de Ingeniería and the SECyT of the Universidad Nacional del Centro de la Provincia de Buenos Aires and the Comisión de Investigaciones Científicas de la Provincia de Buenos Aires (C.I.C.) by their sponsorship.
References and Notes
- Mirífico, M. V.; Cafferata, L. F. R. An. Asoc. Quím. Argent. 1986, 74, 501.
- Mc Cullough, K. J.; Morgan, A. R.; Nonhebel, D. C.; Pauson, P. L.; White, G. J. J. Chem. Res. Synop. 1980, 34, M 0601.
- Riddick, J. A.; Bunger, W. B. Organic Solvent; Vol. II, Weissberger, Ed.; Wiley Interscience: N. Y., 1970. [Google Scholar]
| Solvent | 105 k; s-1 |
| Acetonitrile | 1,46a |
| Dioxane | 1,85 |
| 2-propanol/benzene | 6,9 |
| Benzeneb | 0,51 |
a 153°C
b Ref. (1)
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MDPI and ACS Style
Mateo, C.M.; Cañizo, A.I.; Eyler, G.N. Thermal Decomposition Reaction of Acetophenone Cyclic Diperoxide in Solvents of Different Physicochemical Properties. Molecules 2000, 5, 365-366. https://doi.org/10.3390/50300365
AMA Style
Mateo CM, Cañizo AI, Eyler GN. Thermal Decomposition Reaction of Acetophenone Cyclic Diperoxide in Solvents of Different Physicochemical Properties. Molecules. 2000; 5(3):365-366. https://doi.org/10.3390/50300365
Chicago/Turabian StyleMateo, C. M., A. I. Cañizo, and G. N. Eyler. 2000. "Thermal Decomposition Reaction of Acetophenone Cyclic Diperoxide in Solvents of Different Physicochemical Properties" Molecules 5, no. 3: 365-366. https://doi.org/10.3390/50300365
