DYNAMIC HPLC - A METHOD FOR DETERMINING RATE CONSTANTS, ENERGY BARRIERS, AND EQUILIBRIUM-CONSTANTS OF MOLECULAR DYNAMIC PROCESSES

Kinetic and thermodynamic data for molecular transformations A reversible B with activation energies of 65 to 105 kJ mol-1 can be obtained by simulation of the HPLC chromatogram of mixtures of A and B. This is accomplished by using the retention times, the number of theoretical plates, the asymmetry factors, the initial molar ratios, and the relative sensitivity of the detector, together with trial parameters for the apparent rate constants of the overall forward and reverse reactions. The simulation, in turn, can be used to calculate equilibrium constants and activation energies. A precision of 8% was estimated for this method of simulation.