Journal of Physical Chemistry A, Vol.113, No.27, 7774-7778, 2009
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) approximate to alpha(b) trend. Moreover, the beta angle decreases with increasing temperature. Such anisotropy is consistent with the geometry of the very weak N3 center dot center dot center dot H3 hydrogen bond which acts mainly along the c axis.