The formation of (?h2o2 and GBt was studied in -irradiated aqueous solutions containing selected mixtures of scavengers for both oxidizing and reducing primary free radicals. Experimental verification was made of various assumptions based on the free-radical model of water radiolysis. It was confirmed that efficient scavenging of OH radicals not only reduces GHio2 but also increases GBi by depressing the extent of water reforming reactions and making more eaq-available for increased H2 formation. Similarly, it was shown that the removal of eaq~l eads not only to a decrease in GBi but also to an increase in Gh2o". These effects are additive, and empirical relations were proposed to correlate the expected primary molecular yields with the reactivities toward OH and eaq-. Unifying curves were obtained for the dependence of observed fractional yield changes, on reactivities. They point out that the secondary spur reactions of radicals with products of radical-solute scavenging reactions are rather exceptions even at solute concentrations of about 1M and reactivities of 1010 sec-1.Interlamellar Metal Complexes on Layer Silicates. I. Copper(II)-AreneComplexes on Montmorillonite

The RRKM calculations were performed using an exact count calculation for the sum of states at low E+. The Haarhoff approximation32 was used for the density of states of the molecule and the sum of states at high E+ values. The moments of inertia for the complex and molecule were assumed identical. All overall rotations were assumed adiabatic. A reaction path degeneracy of 2 was employed. 765The model for unimolecular decomposition of CB2 by hydrogen atom rupture was approximated by adding identical frequencies characteristic of a methyl group to both the complex and molecule for propene unimolecular decomposition by hydrogen rupture.28 The e0 was taken as 85 kcal mol"1 and a reaction path degeneracy of 6 was used.

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Abstract. 0 2 -free aqueous solutions of 0.05 mol dm -3 rmmonium bicarbonate were studied after receiving vnrious doses of so Co gammas (0.001-170 Mrd) or krd pulses of 10 MeV electrons. Formate, oxalate, formaldehyde and an unidentified polymer (M W 14000-16000 daltons) were found to be the main radiolytic products. A large initial yield of formate in the Y-radiolysis, G(HC00 -) = 2.2, is due to the reaction CO* + HCO7 t HC00~ + CO3. The efficiency of organic synthesis within the large dose range studied is low and is explained by efficient pathways to the reformation of bicarbonate, where the reaction