Gary L. Bertrand
Professor Emeritus of Chemistry
Missouri University of Science and Technology
(formerly University of Missouri-Rolla)
A First-Order Reaction is described mathematically as:
ln ([A]t) = ln ([A]t=0) - νAkt
The simplest way to confirm that these are the proper equations to describe the reaction and to get an approximate value for k or k', is with the method of half-lives. The half-life t1/2 is defined as the time required for the initial concentration to be halved:
The time required for the concentration to be reduced to 1/4 of the initial concentration (t3/4) is
In a First-Order Reaction, the concentration of the reactant remaining after x half-lives is:
This relationship is unique to First-Order and Pseudo-First-Order Reactions. This may be confirmed either by following concentration in time for a single series of measurements over three or more half-lives, or by comparing the half-lives of different series of measurements in which the initial concentration is varied by a factor of 4 or more. The reaction rate constant may then be calculated from the "best" value of the half-life:
NOTE:The "First-Order Kinetics" exercise is designed so that you can get an accurate value of the half-life. Scan the concentration column for a value slightly larger than half of the initial concentration. Adjust the value of "Start Time" and the value of "Interval" to get a better estimate of the half-life. The same procedure may be used to find the time for the second and third half-lives.
The best values of the reaction rate constant (k) can be obtained with data taken in the middle third of the reaction (from [A]t = (2/3)[A]t=0 to [A]t = (1/3)[A]t=0). Linear Least Squares regression with Y = ln([A]t) and X = t gives - k or - k' as the slope.