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23 Analysis of Kinetics Data

23 Analysis of Kinetics Data

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23
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.
EXPERIMENTAL TECHNIQUES
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 Either a “batch” method can beused, in which samples are withdrawn from the reaction mixture and analyzed,or the reaction may be monitored in situ.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
Excel
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)
 
374Excel for ChemistsFor the reaction of species A to give product B, with rate constant k
k
A-----,Bthe rate of disappearance of A is proportional to the amount of A:4%- = -k[A]tdt(23-l)Of course the rate of appearance of product can also be used to monitor thereaction, since
-44 t d[Blt--
dt-dtIntegration of equation 23-1 leads to the relationshipln Plt =- kt + In [Alo
orlog Mt =
-2.303 k t + log [A]0(23-2)that is, a plot of the logarithm of the concentration of A, plotted vs. time, yields astraight line from which the rate constant k can be obtained. The intercept term isusuallv of no interest.An alternative form of equation 23-1 that sometimes is useful is[A]t = [A]oemkt(23-3)Occasionally a first-order rate constant is obtained by experimentaldetermination of the half-life tin the time required for the reactant concentrationto decrease to one-half of its original value. From equation 23-2 it follows that k =ln(2)/tl/2 = 0.693&/L.If a reaction is monitored by UV-visible spectrophotometry, for example, theconcentration may be replaced by the absorbance (A) in equation 23-2. In thegeneral case, both reactant and product may absorb at the monitoringwavelength, and thus the final absorbance is non-zero. Under these conditionsthe form of equation 23-4 that must be used isInIAt-A-1 = -kt+hIAi-A-1 (23-4)where Ai is the initial absorbance reading and A, is the absorbance value whenthe reaction is “complete”. For first-order reactions the rule of thumb is that 10half-lives must elapse before the reaction can be considered to be complete. After10 half-lives a first-order reaction is (1 - 0.51°) or 99.9% complete.Figure 23-l illustrates the application of equation 23-4 in the determination ofthe hydrolysis of a substrate by the enzyme thermolysin. The parameters
 
Chapter 23Analysis of Kinetics Data375returned by the SLOPE and INTERCEPT functions were used to calculate thetheoretical line in column D of Figure 23-l. The formula in cell D8 is=$B$26+A8*$B$25.The first-order behavior is verified by the straight-line fit of the data, shownin Figure 23-2.
AMA]
bu
Thlermdusin
1.3678
1.292
; ..._“I .1 ki’1.4441.167
1.437
12 I.201141.15816031.138.,1 .121.9772.2472.517.A............ ...2.787
1
,2fir:i 1
.‘.
.::./INTERC=EPT=’ 0.35708’031 * ““.
Figure 23-l. Data table for the enzymatic hydrolysis of FAGLA by thermolysin.

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