Oxygen entry rate

Table 9.9. Oxygen entry rate (k ), exit rate (k ) and migration rate (x) determined on - ...

Solids discharge in the underflow slurry is performed in either an open or a closed system. With the open system, the slurry is rejected through an adjustable orifice at the apex of the cone to an open trough. The orifice can be adjusted to regulate the flow rate of the water leaving with the solids. The open system can allow oxygen entry into the system. 

Entry 3 has only alkyl substituents and yet has a significant lifetime in the absence of oxygen. The tris(/-butyl)methyl radical has an even longer lifetime, with a half-life of about 20 min at 25°C. The steric hindrance provided by the /-butyl substituents greatly retards the rates of dimerization and disproportionation of these radicals. They remain highly reactive toward oxygen, however. The term persistent radicals is used to describe these species, because their extended lifetimes have more to do with kinetic factors than with inherent stability." Entry 5 is a sterically hindered perfluorinated radical and is even more long-lived than similar alkyl radicals. 

Mercury point sources and rates of particle scavenging are key factors in atmospheric transport rates to sites of methylation and subsequent entry into the marine food chain (Rolfhus and Fitzgerald 1995). Airborne soot particles transport mercury into the marine environment either as nuclei for raindrop formation or by direct deposition on water (Rawson etal. 1995). In early 1990, both dimethylmercury and monomethylmercury were found in the subthermocline waters of the equatorial Pacific Ocean the formation of these alkylmercury species in the low oxygen zone suggests that Hg2+ is the most likely substrate (Mason and Fitzgerald 1991 Figure 5.1). 

Aeration was controlled at one of three rates by connecting either a dissolved oxygen (DO) or redox electrode, as appropriate (Section 2.4), to a meter containing a trip amplifier. The trip amplifier operated at two set points and switched two solenoid valves to allow the entry of air at a high or low flow rate through a pipe that emerged under the... 

Moreover, both the as- and trons-aUcenes react at the same rate and yield the same product (Tab. 8.9, entries 1 and 2). As demonstrated above, this was not the case with the N-tethered enynes (Tab. 8.2, entry 6) which gave a mixture of products. Nitrogen-and oxygen-tethered enynes were subjected to the rhodium(I) conditions affording high yields of the halogen shift product (Tab. 8.9, entries 1-10). 

The acidity constants of protonated ketones, pA %, are needed to determine the free energy of reaction associated with the rate constants ArG° = 2.3RT(pKe + pK ). Most ketones are very weak bases, pAT < 0, so that the acidity constant K b cannot be determined from the pi I rate profile in the range 1 < PH <13 (see Equation (11) and Fig. 3). The acidity constants of a few simple ketones were determined in highly concentrated acid solutions.19 Also, carbon protonation of the enols of carboxylates listed in Table 1 (entries cyclopentadienyl 1-carboxylate to phenylcyanoacetate) give the neutral carboxylic acids, the carbon acidities of which are known and are listed in the column headed pA . As can be seen from Fig. 10, the observed rate constants k, k for carbon protonation of these enols (8 data points marked by the symbol in Fig. 10) accurately follow the overall relationship that is defined mostly by the data points for k, and k f. We can thus reverse the process by assuming that the Marcus relationship determined above holds for the protonation of enols and use the experimental rate constants to estimate the acidity constants A e of ketones via the fitted Marcus relation, Equation (19). This procedure indicates, for example, that protonated 2,4-cyclohexadienone is less acidic than simple oxygen-protonated ketones, pA = —1.3. 

---