Radical equilibrium studies. II. The thermodynamic parameters of s−butyl

✍ Scribed by Roger M. Marshall; Nicholas D. Page

• Book ID: 102929824
• Publisher: John Wiley and Sons
• Year: 1979
• Tongue: English
• Weight: 801 KB
• Volume: 11
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550110211

✦ Synopsis

The thermal decomposition of azomethane in the presence of propene has been investigated in the range of 568438°K a t reactant partial pressures of up to about 7 torr in the presence of a t least 170 torr of argon. The elementary reactions taking place in such conditions are discussed in detail. It is shown that a situation approaching equilibrium is attained between the processes

Values are obtained for the equilibrium constant K:!, which can be described by the equation log K:! (atm) = 7.66 -26.1 kcal/mol/(2.3RT) Using the best available thermodynamic parameters for methyl and propene, it is concluded that those for s-butyl are in need of adjustment. We recommend the values (300°K) = 13.8 f 1.0 kcal/mol and Sgm (1 atm standard state) = 75.6 f 3.0 cal/mol-K together with group additivity values of the heat capacity. A comparison of measured values of K:! with values calculated from independent measurements of k:! and k-2 shows a discrepancy of about a factor of 3.5.