Kinetics of alpha-PcCu --> beta-PcCu isothermal conversion in air and thermal behavior of beta-PcCu from in situ real-time laboratory parallel-beam X-ray powder diffraction.
The kinetics of the alpha-PcCu --> beta-PcCu conversion in air has been followed, under isothermal conditions, in situ real-time in the 423-443 K temperature range. Data have been fitted following the JMAK model. The reaction order of the kinetics at 423 K is consistent with a diffusion controlled, deceleratory nucleation rate process for 2D laminar particles, whereas at higher temperatures it is consistent with a phase boundary controlled, deceleratory nucleation rate process for 2D laminar particles. At 423 K, the overall transformation mechanism implies three steps: growth of the alpha-PcCu phase, disordering of adjacent columns of molecules of phthalocyanine, and nucleation and growth of the beta-PcCu phase. The calculated empirical activation energy is of 187 kJ/mol significantly greater than that for the alpha-PcCo --> beta-PcCo conversion. This fact seems to support the reported different structures of alpha-PcCo and alpha-PcCu. Investigation of the thermal behavior of beta-PcCu indicates a strongly anisotropic thermal expansion that follows the alpha(c) >> alpha(a) approximately = alpha(b) trend. Moreover, the beta angle decreases with increasing temperature. Such anisotropy is consistent with the geometry of the very weak N3...H3 hydrogen bond which acts mainly along the c axis.
Ballirano
Paolo
P
Dipartimento di Scienze della Terra Università di Roma La Sapienza, P.le A. Moro 5, I-00185 Roma, Italy. paolo.ballirano@uniroma1.it
Caminiti
Ruggero
R