Diffusion and kinetics of solvent-free reaction between molecular crystals by time-resolved powder UV-Vis reflection spectrum.
Traditionally, chemical reaction between solids has been considered to typically occur on a geological time scale without the benefit of high temperature, due to diffusion block in the solids. However, recent advancements have revealed that many solvent-free reactions between molecular crystals can quickly occur at room or near-room temperature. These reactions have raised a novel scientific question as to how the reactive species can overcome the diffusion-controlled kinetic limitations under such moderate conditions. From time-resolved powder UV-vis reflection spectra and optical micrographs with the reaction between dimethylglyoxime and Ni(Ac) 2.4H 2O and the reaction between hexamethylenetetramine and CoCl 2.6H 2O as models, we found that the solvent-free reaction really occurs at an intermediate state between the solid state and the liquid state. Formation of the liquid phase provides a convenient approach to diffusion of reactive species, whereas formation of a solid product layer hampered the transfer of reactive species. Both factors led to a broad reactive rate band in the long reaction region. The results have explained the diffusion mechanism of the fast reaction between the molecular crystals under moderate conditions.
Tang
Xin-Cun
XC
College of Chemistry and Chemical Engineering, Center South University, Changsha 410083, China. tangxincun@163.com
Jia
Dian-Zeng
DZ
Jiang
Chen-Kui
CK
Jiang
Li-Hui
LH
Guo
Zai-Ping
ZP