Lundberg-type Bounds and Asymptotics for the Moments of the Time to Ruin

We obtain analogues of Lundberg’s inequality and the Cramér—Lundberg asymptotic relationship for the k-th moment of the time to ruin in the classical risk model. We also derive the asymptotic behaviour of the mean time to ruin when the claim size distribution has a heavy or intermediate tail.     

Rate constants for the gas-phase reactions of O3 with selected organics at 296 K

Rate constants for the gas-phase reactions of O₃ with ethene, propene, 1-hexene, 1-heptene, styrene, o-, m-, and p-cresol, o- and m-xylene, benzylchloride, acrylonitrile, and trichloroethene have been determined at 296 ± 2 K. The rate constants ranged from <5 × 10^?21 cm³ molecule^?1 s^?1 for m-xylene to 2.16 × 10^?17 cm³ molecule^?1 s^?1 for styrene, with those for ethene, propene, and 1-hexene being in excellent agreement with literature data.     

Computer modeling of smog chamber data: Progress in validation of a detailed mechanism for the photooxidation of propene and n-butane in photochemical smog

A detailed mechanism is presented for reactions occurring during irradiation of part-per-million concentrations of propene and/or n-butane and oxides of nitrogen in air. Data from an extensive series of well-characterized smog chamber experiments carried out in our 5800-liter evacuable chamber–solar simulator facility designed for providing data suitable for quantitative model validation were used to elucidate several unknown or uncertain kinetic parameters and details of the reaction mechanism. The mechanism was then tested against the data base from the smog chamber runs. In general, most calculated concentration–time profiles agreed with experiments to within the experimental uncertainties. Fits were usually attained to within ～±20% or better for ozone, NO, propene, and n-butane, to within ～±30% or better for NO₂, PAN, methyl ethyl ketone, 2-butyl nitrate, butyraldehyde, and (in runs not containing propene) methyl nitrate, to within ?±50% or better for the minor products 1-butyl nitrate and propene oxide, and to within a factor of 2 for methyl nitrate in propene-containing runs. Propionaldehyde was consistently underpredicted in all runs; it is probably a chamber contaminant. For formaldehyde and acetaldehyde, the major products in both systems, fits to within ?±20% were often obtained, yet for a number of experiments, significantly greater discrepancies were observed, probably as a result of experimental and/or analytical problems. The good fits to experimental data were attained only after adjusting several rate constants or rate constant ratios related to uncertainties concerning chamber effects or the chemical mechanism. The largest uncertainty concerns the necessity to include in the mechanism a significant rate of radical input from unknown sources in the smog chamber. Other areas where fundamental kinetic and mechanistic data are most needed before a predictive, detailed propene + n-butane-NO_x-air smog model can be completely validated concern other chamber effects, the O₃ + propene mechanism, decomposition rates of substituted alkoxy radicals, primary quantum yields for radical production as a function of wavelength for aldehyde and ketone photolyses, and the mechanisms and rates of reactions of peroxy radicals with NO and NO².     

Rate constants for the gas-phase reactions of O3 with a series of carbonyls at 296 K

Rate constants for the gas-phase reactions of O₃ with the carbonyls acrolein, crotonaldehyde, methacrolein, methylvinylketone, 3-penten-2-one, 2-cyclohexen-1-one, acetaldehyde, and methylglyoxal have been determined at 296 ± 2 K. The rate constants ranged from <6 × 10^?21 cm³ molecule^?1 s^?1 for acetaldehyde to 2.13 × 10^?17 cm³ molecule^?1 s^?1 for 3-penten-2-one. The substituent effects of ? CHO and CH₃CO? groups on the rate constants are assessed and discussed, as are implications for the atmospheric chemistry of the natural hydrocarbon isoprene.     

In situ formation of ruthenium catalysts for the homogeneous hydrogenation of carbon dioxide

A total of 44 different phosphines were tested, in combination with [RuCl(2)(C(6)H(6))](2) and three other Ru(II) precursors, for their ability to form active catalysts for the hydrogenation of CO(2) to formic acid. Half (22) of the ligands formed catalysts of significant activity, and only 6 resulted in very high rates of production of formic acid. These were PMe(3), PPhMe(2), dppm, dppe, and cis- and trans-Ph(2)PCH=CHPPh(2). The in situ catalysts prepared from [RuCl(2)(C(6)H(6))](2) and any of these 6 phosphine ligands were found to be at least as efficient as the isolated catalyst RuCl(O(2)CMe)(PMe(3))(4). There was no correlation between the basicity of monophosphines (PR(3)) and the activity of the catalysts formed from them. However, weakly basic diphosphines formed highly active catalysts only if their bite angles were small, while more strongly basic diphosphines had the opposite trend. In situ (31)P NMR spectroscopy showed that trans-Ru(H)(2)(dppm)(2), trans-RuCl(2)(dppm)(2), trans-RuHCl(dppm)(2), cis-Ru(H)(O(2)CH)(dppm)(2), and cis-Ru(O(2)CH)(2)(dppm)(2) are produced as the major metal-containing species in reactions of dppm with [RuCl(2)(C(6)H(6))](2) under catalytic conditions at 50 degrees C.     

Effects of ring strain on gas-phase rate constants. I. Ozone reactions with cycloalkenes

Rate constants for the gas-phase reactions of O₃ with a series of cycloalkenes and with cis-2-butene have been determined at 297 ± 1 K. The rate constants obtained were (in units of 10^?16 cm³/molecule·s): cis-2-butene, 1.38 ± 0.16; cyclopentene, 2.75 ± 0.33; cyclohexene, 1.04 ± 0.14; cycloheptene, 3.19 ± 0.36; 1,3-cyclohexadiene, 19.7 ± 2.8; 1,4-cyclohexadiene, 0.639 ± 0.074; bicyclo[2.2.1]-2-heptene, 21.4 ± 3.5; bicyclo[2.2.1]-2,5-heptadiene, 46.8 ± 12.9; and bicyclo[2.2.2]-2-octene, 0.728 ± 0.090. These data for cis-2-butene, cyclopentene, and cyclohexene are compared with previous literature data, and the effects of ring strain on the rate constants are discussed.     

Synthesis of 4-azacyclopent-2-enones and 5,5-dialkyl-4-azacyclopent-2-enones

Three different methods are reported for the preparation of 4-azacyclo-2-enones 1, two of which allow the preparation of the compounds in optically active form. In addition, a facile route to 4-aza-5,5-dimethylcyclopent-2-enones 2 is disclosed.     

Kinetics of the gas-phase reactions of OH radicals with a series of α,β-unsaturated carbonyls at 299 ± 2 K

Relative rate constants for the reaction of OH radicals with a series of α,β-unsaturated carbonyls have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with propene of 2.52 × 10^?11 cm³/molec·s, the rate constants obtained are (× 10¹¹ cm³/molec·s: acrolein, 1.83 ± 0.13; crotonaldehyde, 3.50 ± 0.40; methacrolein, 2.85 ± 0.23; and methylvinylketone, 1.88 ± 0.14). These data, which are necessary input to chemical computer models of the NO_x–air photooxidations of conjugated dialkenes, are discussed and compared with literature values.     

Steam chugging in a boiling water reactor pressure-suppression system

Results of a transient analysis predicting the general characteristics of steam chugging compare well with the results of two large scale experiments: GKM II, test 21 and GKSS, test 16. Predicted fundamental periods of chugging are within 5 and 16 per cent of the respective experimental values. The results of the analysis include effects of air in the drywell, momentum loss and heat transfer in the condensation pipe, direct contact condensation heat transfer at the gas-water interface and momentum and heat transfer in the wetwell water pool. Bubble shape is calculated in two-dimensional cylindrical coordinates.Required inputs to the analysis include the geometry, initial conditions and constants to determine both the steam inlet mass flowrate to the drywell as a function of time and conduction heat transfer through the wall of the condensation pipe. There are no arbitrary free parameters which must be specified to predict specific experiments. Rather, the analysis is based on fundamental physical phenomena, experimental coefficients documented for general heat transfer and fluid mechanics characteristics and standard analytical techniques.The random nature of steam chugging observed in some experiments is partially explained by predicted regimes of chugging and changes in the maximum extent of a bubble below the condensation pipe exit during each regime.