Study on the Melting Mechanism of Maleic Anhydride

Author(s): Bratati Das, Ashis Bhattacharjee*

Journal Name: Current Physical Chemistry

Volume 10 , Issue 1 , 2020

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Graphical Abstract:


Background: Melting of a pure crystalline material is generally treated thermodynamically which disregards the dynamic aspects of the melting process. According to the kinetic phenomenon, any process should be characterized by activation energy and preexponential factor where these kinetic parameters are derivable from the temperature dependence of the process rate. Study on such dependence in case of melting of a pure crystalline solid gives rise to a challenge as such melting occurs at a particular temperature only. The temperature region of melting of pure crystalline solid cannot be extended beyond this temperature making it difficult to explore the temperature dependence of the melting rate and consequently the derivation of the related kinetic parameters.

Objective: The present study aims to explore the mechanism of the melting process of maleic anhydride in the framework of phase transition models. Taking this process as just another first-order phase transition, occurring through the formation of nuclei of new phase and their growth, particular focus is on the nucleation and growth models.

Methods: Non-isothermal thermogravimetry, as well as differential scanning calorimetry studies, has been performed. Using isoconversional kinetic analysis, temperature dependence of the activation energy of melting has been obtained. Nucleation and growth models have been utilized to obtain the theoretical temperature dependencies for the activation energy of melting and these dependencies are then compared with the experimentally estimated ones.

Conclusion: The thermogravimetry study indicates that melting is followed by concomitant evaporation, whereas the differential scanning calorimetry study shows that the two processes appear in two different temperature regions, and these differences observed may be due to the applied experimental conditions. From the statistical analysis, the growth model seems more suitable than the nucleation model for the interpretation of the melting mechanism of the maleic anhydride crystals.

Keywords: Differential scanning calorimetry, isoconversional kinetics, maleic anhydride, melting mechanism, thermogravimetry, acid anhydride.

Trivedi, B.C.; Culbertson, B.M. Maleic Anhydride; Springer, Science + Bussiness Media, NY,, 1982.
Back, R.A.; Parsons, J.M. The thermal and photochemical decomposition of maleic anhydride in the gas phase. Can. J. Chem., 1981, 59, 1342-1346.
Tammann, G. The States of Aggregation; Van Nostrand: New York, 1925.
Cormia, R.L.; Mackenzie, J.D.; Turnbull, D. Kinetics of melting and crystallization of phosphorus pentoxide. J. Appl. Phys., 1963, 34, 2239-2244.
Tromp, R.M.; Hannon, J.B. Thermodynamics of nucleation and growth. Surf. Rev. Lett., 2002, 9, 1565-1593.
Saka, H.; Nishikawa, Y.; Imura, T. Melting temperature of in particles embedded in an Al matrix. Philos. Mag. Lett., 1988, 57, 895-906.
Toda, A.; Hikosaka, M.; Yamada, K. Superheating of the melting kinetics in polymer crystals: A possible nucleation mechanism. Polymer (Guildf.), 2002, 43, 1667-1679.
Stanford, V.L.; McCulley, C.M.; Vyazovkin, S. Isoconversional kinetics of nonisothermal crystallization of salts from solutions. J. Phys. Chem. B, 2016, 120(25), 5703-5709.
[] [PMID: 27305831]
Vyazovkin, S.; Yancey, B.; Walker, K. Polymer melting kinetics appears to be driven by heterogeneous nucleation. Macromol. Chem. Phys., 2014, 215, 205-209.
Liavitskaya, T.; Birx, L.; Vyazovkin, S. Melting kinetics of superheated crystals of glucose and fructose. Phys. Chem. Chem. Phys., 2017, 19(38), 26056-26064.
[] [PMID: 28926042]
Šesták, J. Thermophysical properties of solids, their measurements and theoretical analysis; Elsevier: Amsterdam, 1984, Vol. 12D, .
Cordes, H.F. Pre-exponential factors for solid-state thermal decomposition. J. Phys. Chem., 1968, 72, 2185-2189.
Rooj, A.; Roy, M.; Bhattacharjee, A. Thermal decomposition reaction of ferrocene in the presence of oxalic acid. Int. J. Chem. Kinet., 2017, 49, 319.
Vyazovkin, S. Modification of the integral isoconversional method to account for variation in the activation energy. J. Comput. Chem., 2001, 22, 178.
Bērziņš, A.; Actiņš, A. Evaluation of kinetic parameter, calculation methods for non-isothermal experiments in case of varying activation energy in solid-state transformations. Latvian J. Chem., 2012, 51, 209-227.
Papon, P.; Leblond, J.; Meijer, P.H.E. The Physics of Phase Transitions; Berlin Heidelberg, Springer- Verlag: Germany, 2002, p. 185-209.
Turnbull, D.; Fisher, J.C. Rate of nucleation in condensed Systems. J. Chem. Phys., 1949, 17, 71-73.
Vyazovkin, S. Isoconversional kinetics of thermally stimulated processes; Springer: Heidelberg, 2015.
Mullin, J.W. Crystallization, 4th ed; Elsevier Butterworth-Heinemann: Oxford, 2004.
Mandelkern, L. Kinetics and mechanisms, crystallization of polymers; Cambridge University Press: Cambridge, 2004, Vol. 2, .
Christian, J.W. The Theory of transformations in metals and alloys; Pergamon: Amsterdam, 2002.
Ainslie, N.G.; Mackenzie, J.D.; Turnbull, D. Melting kinetics of quartz and cristobalite. J. Phys. Chem., 1961, 65, 1718-1724.
Illers, K.H. The determination of the melting point of the crystalline polymer by calorimetry. Eur. Polym. J., 1974, 10, 911-916.
Lippits, D.R.; Rastogi, S.; Höhne, G.W.H. Melting kinetics in polymers. Phys. Rev. Lett., 2006, 96(21), 218303-218306.
[] [PMID: 16803278]
Chen, K.; Baker, A.N.; Vyazovkin, S. Formation and thermal behaviour of polystyrene and polystyrene/clay gels. Macromol. Chem. Phys., 2008, 209, 2367-2373.
Dranca, I.; Vyazovkin, S. Thermal stability of gelatine gels: Effect of preparation conditions on the activation energy barrier to melting. Polymer (Guildf.), 2009, 50, 4859-4867.
Cubeta, U.; Bhattacharya, D.; Sadtchenko, V. Melting of superheated molecular crystals. J. Chem. Phys., 2017, 147(1), 014505-014513.
[] [PMID: 28688404]
Ubbelohde, A.R. Thermodynamics and the velocity of irreversible processes. Part-II: Chemical reaction velocity. Trans. Faraday Soc., 1937, 33, 1198-1212.
Glasstone, S.; Laidler, K.J.; Eyring, H. The Theory of Rate Processes; McGraw-Hill: New York, 1941.
Frenkel, J. Kinetic Theory of Liquids; Oxford University Press: London, 1946.
Ubbelhode, A.R. The Molten State of Matter; Wiley: Chichester, 1978.
Wunderlich, B. Crystal Melting, Macromolecular Physics; Academic Press: New York, 1980, Vol. 3, .
Sasaki, K.; Saka, H. In situ high-resolution electron microscopy observation of the melting process of In particles embedded in an Al matrix. Philos. Mag. A Phys. Condens. Matter Defects Mech. Prop., 1991, 63, 1207-1220.
Johnson, E.; Dahmen, U. In situ transmission electron microscopy observations of alloying of nanoscale Pb inclusions by implantation with Cd Ions. Microsc. Microanal., 1997, 3, 409-416.

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Article Details

Year: 2020
Published on: 29 January, 2020
Page: [65 - 78]
Pages: 14
DOI: 10.2174/1877946809666191011155328

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