On the Sick Father, the Repentant Sinner, and Other Problems in Medieval Deontic Logic

Many medieval philosophers and logicians regarded modal logic as a model for epistemic, normative and optative concepts on the basis of their apparent similarities to modal concepts. These interpretations of modal logic led to critical studies of the applicability of modal principles to deontic concepts. Some philosophers presented apparent counterexamples to the deontic interpretation of the Consequence Principle, according to which the consequences of what is obligatory (or permitted) are also obligatory (permitted). These examples are variants of Lennart Åqvist's paradox of the Good Samaritan. In this article it is argued that the examples involve a confusion between the compounded and the divided senses of deontic propositions, and are not genuine counterexamples to the Consequence Principle. If the concept of knowledge is analysed as epistemically satisfactory belief, the paradox of epistemic obligation can be solved in a similar way

Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with nitric oxide

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with NO. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas at five temperatures in the range 299-592 K. The second-order rate constants at 10 Torr fitted the Arrhenius equation log(k/cm3 molecule-1 s-1) = (-11.66 ± 0.01) + (6.20 ± 0.10 kJ mol-1)/RT ln 10 The rate constants showed a variation with pressure of a factor of ca. 2 over the available range, almost independent of temperature. The data could not be fitted by RRKM calculations to a simple third body assisted association reaction alone. However, a mechanistic model with an additional (pressure independent) side channel gave a reasonable fit to the data. Ab initio calculations at the G3 level supported a mechanism in which the initial adduct, bent H2SiNO, can ring close to form cyclo-H2SiNO, which is partially collisionally stabilized. In addition, bent H2SiNO can undergo a low barrier isomerization reaction leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are NH2 + SiO. The rate controlling barrier for this latter pathway is only 16 kJ mol-1 below the energy of SiH2 + NO. This is consistent with the kinetic findings. A particular outcome of this work is that, despite the pressure dependence and the effects of the secondary barrier (in the side reaction), the initial encounter of SiH2 with NO occurs at the collision rate. Thus, silylene can be as reactive with odd electron molecules as with many even electron species. Some comparisons are drawn with the reactions of CH2 + NO and SiCl2 + NO