title: Theoretical basis for the detection of general-base catalysis in the presence of predominating hydroxide catalysis.
abstract: The detection of general-base catalysis in the presence of predominating specific-base catalysis in aqueous buffer solutions is examined for various relationships between k0cat and k0OH, the bimolecular rate constants for general-base and hydroxide-ion attack. The three experimental variables that affect the detection of buffer-base catalysis are the type of buffer, conjugate-acid concentration, and ionic strength. Various buffers used in pharmaceutical kinetic studies are considered, and it is concluded that buffers with high Ka values favor detection. Additionally, high conjugate-acid concentrations and ionic strengths appear to optimize the detection of general-base catalysis.
mesh_terms: D000468:Alkalies; D002021:Buffers; D002384:Catalysis; D055598:Chemical Phenomena; D002626:Chemistry, Pharmaceutical; D002627:Chemistry, Physical; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008956:Models, Chemical
chemical_list: D000468:Alkalies; D002021:Buffers