Oxidations by plutonium

The interaction of Pu(VI) and Pu(III) is insignificant. From absorbance-time data for Pu02 at 830 m/i 

The inverse hydrogen-ion dependence of the rate of reaction (13.22) is exceptionally complex and is summarised by 

Likewise, chloride ion has a marked accelerating effect on the two-equivalent reduction of Pu(VI) by Sn(II). On the assumption that the rate-determining step is 

Neither of these possibilities are likely the disproportionation of Pu(V), and the Pu(V)+Sn(II) reaction are too slow to account for the rapidity and kinetics of the overall reaction. That the Pu(VI)+Sn(II) reaction is very much faster than the Pu(V)+Sn(II) reduction is taken as evidence for the occurrence of a single two-equivalent process, viz. 

The chloride-ion dependence indicates the importance of two activated complexes, (PuOjSnCls y and (Pu02SnCl4), with AH values of 14.0 and 14.6 kcal.mole and AS values of 4.4+7 and 8.0+5.5 cal.deg . mole respectively (as recalculated by Newton and Baker °). In terms of the apparent rate coefficient, k  

---