ANALYSIS OF KINETICS DATA
In this chapter you’ll learn how to extract rate constant information fromsimple first-order processes, from biphasic processes and from complex rateprocesses.
In principle, any measurable property of a reacting system that isproportional to the extent of reaction may be used to monitor the progress of thereaction. The most common techniques are spectrophotometric (UV-visible,fluorescence, IR, polarimetry and NMR) or electrochemical (pH, ion-selectiveelectrodes, conductivity and polarography). Either a “batch” method can beused, in which samples are withdrawn from the reaction mixture and analyzed,or the reaction may be monitored in situ. By far the most widely used techniqueinvolves UV-visible spectrophotometry.Since reaction rate is sensitive to temperature, the system must bethermostatted. For most reactions in aqueous solution, the ionic strength shouldbe controlled at a fixed value (see “Experimental Techniques” in Chapter 22).
ANALYSIS 0~ M~N~PHA~IC KINETICS DATA
Most reactions are characterized by a change in reactant or productconcentration that can be described by a single exponential. The differential formof the rate equation contains a single term; the integrated form yields a straightline from which the rate constant can be obtained. Some of the more commonand useful cases are described.FIRST-ORDER KINETICSFirst-order reactions are by far the most common. They are also the simplestto study experimentally. For reactions of higher order, experimental conditionscan usually be arranged so that they are first-order (see below). This simplifiesthe situation considerably.373
for Chemists: A Comprehensive Guide.
E. Joseph BilloCopyright
2001 by John Wiley & Sons, Inc.ISBNs: 0-471-39462-9 (Paperback); 0-471-22058-2 (Electronic)