𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Laser-induced kinetics: Arrhenius parameters for t-C4H9 + XI → i-C4H9X + I (X = H,D) and the Heat of Formation of the t-butyl radical

✍ Scribed by M. J. Rossi; D. M. Golden

Publisher
John Wiley and Sons
Year
1983
Tongue
English
Weight
886 KB
Volume
15
Category
Article
ISSN
0538-8066

No coin nor oath required. For personal study only.

✦ Synopsis

The metathesis reaction of DI with t X4H9 generated by 351-nm photolysis of 2,2'-azoisopropane was studied in a low-pressure reactor (VLP@ Knudsen cell) in the temperature range of 302-411 K. The data obeyed the following Arrhenius relation when combined with recent data by Rossi and Golden gathered by the same technique (t-CdHg by thermal decomposition of 2,2'-azoisobutane): log kF(M-1.8-1) = 9.60 -1.90/0, where I9 = 2.303RT kcal/mol for 302 K < T < 722 K. The metathesis reaction of HI with t-C,Hg was studied at 301 K and resulted in k?(M-'.s-') = (3.20 f 0.62) X 108. An analogous Arrhenius relation was calculated for the protiated system if the small primary isotope effect kF/kB was assumed to be 4 at 700 K. It was of the following form: log kF(M-'.s-') = 9.73 -1.68/8. Preliminary data of Bracey and Walsh indicate that earlier Arrhenius parameters determined for the reverse reaction are somewhat in error. Their value of log kl(M-'.s-') = 11.5 -23.8/8 yields AHy,300(t -butyl) = 9.2 kcal/mol and S&(t-butyl) = 74.2 cal/mol-K when taken in conjunction with this study.

📜 SIMILAR VOLUMES

The absolute rate constant for the metat
The absolute rate constant for the metathesis t-C4H9• + DI → C4H9D + I• and the heat of formation of the t-butyl radical
✍ Michel Rossi; David M. Golden 📂 Article 📅 1979 🏛 John Wiley and Sons 🌐 English ⚖ 419 KB 👁 1 views

The Arrhenius parameters for the title reaction have been measured in a very-low-pressure pyrolysis apparatus in the temperature range 644-722 K and are given by log kZ (A4-I. sec-I) = 9.68 -2.12/8, where 0 = 2.303RT in kcal/mol. Together with the published Arrhenius parameters for the reverse react

The rate constant for t-C4H9 → H + i-C4H
The rate constant for t-C4H9 → H + i-C4H8 and the thermodynamic parameters of t-C4H9
✍ Carlos E. Canosa; Roger M. Marshall 📂 Article 📅 1981 🏛 John Wiley and Sons 🌐 English ⚖ 565 KB

## Abstract The rate of the reverse reaction of the system equation image has been measured in the range of 584–604 K from a study of the azomethane sensitized pyrolysis of isobutane. Assuming the published value for the rate constant of recombination of __t__‐butyl we obtain Combination with o

Rates and equilibria in the reaction sys
Rates and equilibria in the reaction system Br + i-C4H10 ⇌ HBr + t-C4H9. The heat of formation of the t-butyl radical
✍ Tajmeri S. A. Islam; Sidney W. Benson 📂 Article 📅 1984 🏛 John Wiley and Sons 🌐 English ⚖ 635 KB

The very low pressure reactor (VLPR) technique has been used to measure the bimolecular rate constant of the title reaction at 300 K. The rate constant is given by log k, (l/mol s) = (11.6 2 0.4) -(5.9 ? 0.6)/0 the equilibrium constant has also been measured at the same temperature and is given by K

Structural Characterization and Intramol
Structural Characterization and Intramolecular Aliphatic C−H Oxidation Ability of MIII(μ-O)2MIII Complexes of Ni and Co with the Hydrotris(3,5-dialkyl-4-X-pyrazolyl)borate Ligands Tp3.0.CO;2-C/asset/equation/tex2gif-sup-3.gif?v=1&t=h5lp536o&s=a03c9eb1fe277a993afb16d61a4b5e5e1fd6ae14" class="inlineGraphic"> (X=Me, H, Br) and Tp3.0.CO;2-C/asset/equation/tex2gif-sup-4.gif?v=1&t=h5lp536o&s=f62756419e66415fd41eb92c51dc480468265b22" class="inlineGraphic">
✍ Shiro Hikichi; Michito Yoshizawa; Yasuyuki Sasakura; Hidehito Komatsuzaki; Yoshi 📂 Article 📅 2001 🏛 John Wiley and Sons 🌐 English ⚖ 531 KB

The nickel complex 2 Ni shows reactivity about 10 3 times greater than that of the cobalt analogue 2 Co . The oxidation ability of the M III (m-O) 2 M III core should be affected by the hindered Tp R ligand system, which can stabilize the 2 oxidation state of the metal centers.

An ab initio study of the structures and
An ab initio study of the structures and properties of the XH3.0.CO;2-6/asset/equation/tex2gif-stack-1.gif?v=1&t=h5o1u01t&s=f0564d329b3a20ba93f50bb114b0b5f43bd4e66a" class="inlineGraphic"> and XH3.0.CO;2-6/asset/equation/tex2gif-stack-2.gif?v=1&t=h5o1u01t&s=3028c085e80f7af45e0c371525a02839db9e470b" class="inlineGraphic"> (X=C, Si, Ge) dications
✍ Peter Babinec; Jerzy Leszczynski 📂 Article 📅 1999 🏛 John Wiley and Sons 🌐 English ⚖ 206 KB 👁 3 views

The ab initio electronic structure calculations at the MP2 and the Becke Ž . 3LYP density functional levels in conjunction with the 6-311qqG 2 df, 2 pd basis set were used for the determination of the structure, vibrational spectra, and dissociation 2q 2q Ž . energies of the XH and XH X s C, Si, Ge