The kinetics and solvent effects on the thermal decomposition of isopropyl peroxide and 1, 2-dioxane

Rates of H2 formation have been determined for the thermal decomposition of isopropyl peroxide at l30o-l50oC in toluene and methanol and at l400C in isopropyl alcohol and water. Product studies have been carried out at l400C in these solvents. The decomposition of isopropyl peroxide was shown to be unimolecular with energies of activation in toluene, and methanol of 39.1, 23.08 Kcal/mole respectively. It has been shown that the rates of H2 formation in decomposition of isopropyl peroxide are solvent dependent and that the ~ vs "'2';' values (parameters for solvent polarity) givesastraight line. Mechanisms for hydrogen production are discussed which satisfactorily explain the stabilization of the six-centered transition state by the solvent. One possibility is that of conformation stabilization by solvent and the other, a transition state with sufficient ionic character to be stabilized by a polar solvent. Rates of thermal decomposition of 1,2-dioxane in tert-butylbenzene at l40o-l70oC have been determined. The activation energy was found to be 33.4 Kcal/mole. This lower activation energy, compared to that for the decomposition of isopropyl peroxide in toluene (39.1 Kcal/mole) has been explained in terms of ring strain. Decomposition of 1,2 dioxane in MeOH does not follow a first order reaction. Several mechanisms have been suggested for the products observed for decomposition of 1;2-dioxane in toluene and methanol

Variation in Weed Seed Fate Fed to Different Holstein Cattle Groups

Weed seeds may maintain their viability when passing through the digestive tract of cattle and can be therefore dispersed by animal movement or the application of manure. Whether different cattle types of the same species can cause differential weed seed fate is largely unknown to us particularly under non-grazed systems similar to Holstein-Friesian dairy farming. We investigated the effect on the seed survival of four weed species in the digestive tracts of four groups of Holstein cattle: lactating cows, feedlot male calves, dry cows and growing heifers. The weed species used were Cuscuta campestris, Polygonum aviculare, Rumex crispus and Sorghum halepense. Cattle excretion was sampled for recovery and viability of seeds at four 24 hourly intervals after seed intake. The highest seed recovery occurred two days after seed intake in all cattle groups. Averaged over weed species, dry and lactating cows had the lowest and highest seed recovery of 36.4% and 74.4% respectively. No significant differences were observed in seed recovery of the four weed species when their seeds were fed to dry cows. Based on a power model fitted to seed viability data, the estimated time to 50% viability loss after seed intake, over all cattle groups ranged from 65 h (R. crispus) to 76 h (P. aviculare). Recovered seeds from the dung of feedlot male calves showed the highest mortality among cattle groups. Significant correlation was found between seed viability and ruminal pH (r = 0.86; P<0.05). This study shows that management programs aiming to minimize weed infestation caused by livestock should account for the variation amongst cattle groups in seed persistence. Our findings can be used as a guideline for evaluating the potential risk of the spread of weeds via the application of cattle manure