Abstract
This paper describes and compares performance characteristics of four data-processing options for kinetic-based determinations. Options compared are two-point/fixed-time, one-rate, three-point/fixed-time and two-rate methods. Features evaluated are the effects of systematic changes in variables such as rate constants and reaction order as well as different levels of random noise. Both simulated and experimental data are used to evaluate effects of systematic changes in rate constants and simulated data are used to evaluate effects of random noise and systematic deviations from first-order behavior. All the options appear to be relatively independent of small changes (±0.1) in reaction order. The two-point/fixed-time and one-rate options have no inherent ability to reject effects of systematic changes in rate constants but optimum conditions can be identified that reduce effects of such changes. The latter two methods have the inherent ability to reject effects of systematic changes in rate constants but appear to be more dependent on random noise than the two-point/fixed-time and one-rate options. Application of the optimized two-point/fixed-time and one-rate methods and the three-point/fixed-time and two-rate options to experimental data for uric acid demonstrate 40- to 100-fold improvements in ruggedness for changes in the rate constant relative to non-optimized two-point/fixed-time and one-rate methods.
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