Thermodynamics of porphyrin sublimation
The saturated vapor pressures of tetraphenylporphyrin H 2 TPP , its four-coordinated metallo-complexes MTPP ( M ≡ Ni , Cu , Zn , Pd , Ag , Cd ) and some phenyl-substituted derivatives H 2 T ( R ) PP ( R ≡ 2-, 3-, 4- CH 3; 2-, 4- F ; 2-, 3-, 4- Cl ; 3-, 4- Br ; 3,5- C ( CH 3)3) have been measured using the inert gas flow method. The values of sublimation enthalpy Δ sub H m and entropy Δ sub S m are calculated. On the basis of the kinetic vapor pressure dependence, the start temperatures of thermal destruction of the investigated porphyrins are determined. The temperatures of melting of the tetraphenylporphyrin metallo-complexes measured by the DSC method are in linear correlation with the Δ sub H m values. The correlation between the thermodynamic functions of porphyrin sublimation (Δ sub H m , Δ sub S m , Δ sub G m ) and the literature data on the crystal structure of the compounds is considered. The Δ sub H m values obtained by some authors by different methods are compared with the results of our investigations. Possible reasons for discrepancies in the results are discussed.
A Combined Experimental and Theoretical Study of Nitrofuran Antibiotics: Crystal Structures, DFT Computations, Sublimation and Solution Thermodynamics