The hydrolysis mechanism and kinetic analysis for COS hydrolysis: A DFT study

Аннотация

Density Functional Theory (DFT) was utilized to study the hydrolysis mechanism and kinetic analysis of carbonyl sulfide (COS). The structures of reactants (R), transition states (TS), intermediates (IM) and products (P) were analyzed and a conclusion reached that hydrolysis mechanism of COS occurs in two paths with One path as a C=S path and the other as a C=O path and all featuring potential for forming H₂S and CO₂. Function change analysis of COS hydrolysis indicated the rate-determining step of COS hydrolysis was the first elementary reaction as OH and H in H₂O attacked C=O and S=O in COS, respectively, with the two paths parallel and competitive and the C=S path more reactionary than the C=O path. Influence on each elementary reaction was also not consistent with reaction temperature increase. The study also included further investigation of the COS catalytic hydrolysis.