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At temperatures above 120 °C, the solid-state decomposition of 1 becomes faster than predicted by the Arrhenius equation. A possible explanation is that the dissipation of the resulting heat becomes too slow compared to decomposition rate, eventually leading to the autoacceleration of reaction. No melting occurs even under these conditions, as verified by optical microscopy.
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63
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0343227975
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0,i is set for α = 0.1, the resulting activation energies vary between 14.9 and 24.1 kcal/mol. In comparison, the Avrami-Erofeyev (n = 2) model analysis does not show much variation. Considering also the fact that it fits our data much better than any other model, and is in agreement with the microscopic observations and available structural data for 1, we think that the use of this model is particularly appropriate for the present study.
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64
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0001317391
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For other solid-state reactions where the kinetics are directly coupled to chemical transformations see, for example: (a) Galwey, A. K.; Mohamed, M. A. J. Chem. Soc., Faraday Trans. 1985, 81, 2503. (b) Son, S. F.; Asay, B. W.; Henson, B. F.; Sander, R. K.; Ali, A. N.; Zielinski, P. M.; Phillips, D. S.; Schwarz, R. B.; Skidmore, C. B. J. Phys. Chem. B 1999, 103, 5434.
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Ayala, P.Y.27
Cui, Q.28
Morokuma, K.29
Malick, D.K.30
Rabuck, A.D.31
Raghavachari, K.32
Foresman, J.B.33
Cioslowski, J.34
Ortiz, J.V.35
Stefanov, B.B.36
Liu, G.37
Liashenko, A.38
Piskorz, P.39
Komaromi, I.40
Gomperts, R.41
Martin, R.L.42
Fox, D.J.43
Keith, T.44
Al-Laham, M.A.45
Peng, C.Y.46
Nanayakkara, A.47
Gonzalez, C.48
Challacombe, M.49
Gill, P.M.W.50
Johnson, B.G.51
Chen, W.52
Wong, M.W.53
Andres, J.L.54
Head-Gordon, M.55
Replogle, E.S.56
Pople, J.A.57
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