Resolution of stopped-flow kinetic data for second-order reactions with rate constants up to 108 M-1 s-1 involving large concentration gradients. Experimental comparison using three independent approaches

Journal of Physical Chemistry

Volumn 100, Issue 42, 1996, Pages 16925-16933

  Dunn, Brian C ^a   Meagher, Nancy E ^a   Rorabacher, David B ^a  

^a WAYNE STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001257783     PISSN: 00223654     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp961492y     Document Type: Review

References (21)

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9. Meagher, N. E.; Rorabacher, D. B. J. Phys. Chem. 1994, 98, 12590-12593.
10. The cell filling time was determined by filling one drive syringe with 0.01 M HCl plus phenolphthalein indicator while the other syringe was filled with 0.05 M NaOH. After flushing the cell with either solution, the drive cylinder was activated, and the time required for the transmittance to decrease from 100% to its final constant value was monitored. For recording such measurements the photomultiplier was connected directly to a recording oscilloscope to permit pretrigger record so that the entire filling sequence could be observed.
11. 4 = 1,4,8,11-tetraazacyclotetradecane (cyclam).
12. Meagher, N. E.; Juntunen, K. L.; Salhi, C. A.; Ochrymowycz, L. A.; Rorabacher, D. B. J. Am. Chem. Soc. 1992, 114, 10411-10420.
13. Smith, J. M. Chemical Engineering Kinetics; 3rd ed.; McGraw-Hill: New York, 1981; pp 64-67. Cf.:
14. (a) Pladziewicz, J. R.; Lesniak, J. S.; Abrahamson, A. J. J. Chem. Educ. 1986, 63, 850-851.
15. (b) King, E. L Int. J. Chem. Kinet. 1982, 14, 1285-1286.
16. 12t (see, e.g.: Steinfeld, J. I.; Francisco, J. S.; Hase, W. L. Chemical Kinetics and Dynamics; Prentice-Hall: Englewood Cliffs, NJ, 1989; p 9).
17. If the reverse reaction is not significant. In g = 0 and g = 1 in eqs 5 and 6 (see ref 9).
18. Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265-322.
19. -1, which exceeds the limits of detection for the current instrumentation.
20. 0ka + 1) where a and b represent the times required for the solution to flow from the mixer to the near and far ends of the reaction cell, respectively. The two expressions are seen to contain similar terms but cannot be made identical.
21. Dickson, P. N.; Margerum, D. W. Anal. Chem. 1986, 58, 3153-3158.