Accurate exchange rate constants from valley-to-peak intensity ratios of a two-site system with equal populations
✍ Scribed by Charles L. Perrin
- Publisher
- John Wiley and Sons
- Year
- 1988
- Tongue
- English
- Weight
- 389 KB
- Volume
- 26
- Category
- Article
- ISSN
- 0749-1581
No coin nor oath required. For personal study only.
✦ Synopsis
The valley-to-peak ratio of a 1 : 1 doublet undergoing chemical exchange can be calculated from the line shape equation. Numerical analysis provides a table that permits the evaluation of the rate constant from that ratio. This method is exact, without the approximations of previous equations that suffer from systematic errors. Statistical analysis shows how the experimental error depends on the rate constant and how to weight rate constants of unequal reliability for least-squares analysis. From the tabulated errors it is possible to recognize conditions to optimize the evaluation of rate constants, so that it is realistic to obtain them with a precision of f 1-2%.