Direct evaluation of rate constants for an assumed single-step mechanism from chemical relaxation data

✍ Scribed by Jonathan Victor; David Haselkorn; Israel Pecht

• Publisher: Elsevier Science
• Year: 1973
• Tongue: English
• Weight: 265 KB
• Volume: 6
• Category: Article
• ISSN: 0010-4809
• DOI: 10.1016/0010-4809(73)90051-7

✦ Synopsis

To evaluate chemical relaxation data for an assumed single-step mechanism of the type k12 E+ST ES, linear regression methods are usually applied to the equation describing the concentration dependence of the relaxation time t, l/r = /c&G] + [$I) + k2,. Since calculated values of [,!?I and [s] depend on [E,,], [SO], and K = k12/kz1, this treatment is inappropriate. We present a program which finds the best-fit klz and kzl, directly from the experimental data: l/r, [E,], and [S,]. This is done by treating l/r as a complicated nonlinear function of klz, kzl, [E,,], and [SO], and minimizing R(kmkzt) =-+ (k -+-)'. that the best-fit /c,~ and k,, are calculated without taking into explicit account the