A novel electrochemical method determining pKa and transport parameters of buffers using acid-base transport limitation response

Dissociation constant (logarithmic form, pKa) and diffusion coefficient (D) are two fundamental physical parameters for weak acids and bases (buffers). Their effortless determinations from one method are not available yet. Herein, we propose an innovative method to determine pKa and D values based on a brand-new principle of electrochemical acid-base transport limitation (eABTL). The significance of eABTL lies in its ability to relate inert buffers to electrode reactions, enabling the acquisition of electrochemical responses for inert species. Acid-base transport limiting current (jl) is the only variable that needs to be measured. The pKa and transport coefficient (m) are determined from the relationship of jl vs. solution pH and jl vs. buffer concentration, respectively. Three ways are available for D determinations by introducing the expressions of diffusion layer thickness. The method is demonstrated using rotating disc electrodes to implement hydrogen evolution reaction. The pKa, m and D values exhibit good repeatability in multiple determinations. A well-defined electrode geometry is necessary for accurate D determination. This method can be developed to a family of methods with the advantages for fast estimating practical parameter values of buffers.