An investigation has been made of the reactions of 1hyphen;butene and 2hyphen;butene with mercury (3P1) atoms at 30deg;C in a static system. The main products of the 1hyphen;butene reaction are 2hyphen;butene and liquid polymer. A large number of other products are also formed especially at low pressures. The rate of isomerization increases rapidly with pressure in the region of complete quenching, while the rate of polymerization falls off rapidly. The overhyphen;all rate of consumption of 1hyphen;butene increases very slightly with increasing pressure. The overhyphen;all quantum yield of 1hyphen;butene consumption is 0.32 at 20hyphen;mm pressure. The principal steps in the mechanism proposed for the reaction are:1minus;C4H8plus;Hglpar;3P1rpar;rarr;1minus;C4H8*plus;Hglpar;1Sorpar;,1minus;C4H8*plus;1minus;C4H8rarr;2minus;C4H8plus;1minus;C4H8,1minus;C4H8*rarr;C4H7plus;H,followed by polymerization reactions of the type1minus;C4H8plus;C4H7rarr;C8H15,etc.It is therefore possible for the first time, to obtain a direct measurement of the rate of collisional deactivation merely by determining the rate of formation of 2hyphen;butene. 2hyphen;butene is much less reactive than 1hyphen;butene. The overhyphen;all quantum yield of 2hyphen;butene consumption has a maximum value of 0.11 at an initial pressure of 1ndash;2 mm. Above this pressure the rate of 2hyphen;butene consumption falls off rapidly. The main product of the reaction is a liquid polymer. Smaller amounts of hydrogen and methane are also formed. An activated molecule mechanism is proposed which accounts for the essential aspects of the reaction.
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