The Reaction of Cyclobutane with Hg 6(3P1) Atoms

摘要

The reaction of cyclobutane with Hg 6(3P1) atoms has been studied in a static system at 30.10plusmn;0.01deg;C, over the pressure range from 2ndash;250 mm. The primary products of the reaction are hydrogen,nhyphen;butylcyclobutane, and a saturated C8H14product which is assumed, from kinetic and mass spectral evidence, to be cyclobutylcyclobutane. In addition, prolonged exposure produced a saturated C12H22product which is probably a dicyclobutylbutane.The quantum yields of pressure decrease (phgr;P) hydrogen formation (phgr;H2) and cyclobutane consumption (phgr;C) all reach constant maximum values at cyclobutane pressures greater than approximately 100 mm. These values are phgr;C=0.53, phgr;H2=0.10, and phgr;P=0.16. From the simple stoichiometry of the reaction the quantum yields ofnhyphen;butylcyclobutane (phgr;BC) and cyclobutylcyclobutane (phgr;C2) formation were calculated. From the data phgr;BC=0.16 and phgr;C2=0.10.The following mechanism was found to be consistent with the observed characteristics of the reaction:cyclothinsp;C4H8plus;Hgthinsp;6lpar;3P1rpar;rarr;cyclothinsp;C4H7plus;Hplus;Hgthinsp;6lpar;1S0rpar;,Hplus;cyclothinsp;C4H8rarr;cyclothinsp;C4H7plus;H2,2thinsp;cyclothinsp;C4H7rarr;dicyclothinsp;C8H14,2thinsp;cyclothinsp;C4H7rarr;cyclothinsp;C8H14,Hplus;cyclothinsp;C8H14rarr;cyclothinsp;C8H15,cyclothinsp;C8H15plus;cyclothinsp;C4H8rarr;cyclothinsp;C4H7plus;cyclothinsp;C8H16,where dicyclo C8H14represents cyclobutylcyclobutane; cyclo C8H14, cyclobutylbutene; cyclo C8H15, cyclobutylbutyl radicals; and C8H16,nhyphen;butylcyclobutane. The cyclobutylbutene is considered as an intermediate in the formation of the stablenhyphen;butylcyclobutane product.