Can Indirect Causation be Real?

Causal realists maintain that the causal relation consists in “something more” than its relata. Specifying this relation in nonreductive terms is however notoriously difficult. Michael Tooley has advanced a plausible account avoiding some of the relation’s most obvious difficulties, particularly where these concern the notion of a cross-temporal “connection.” His account distinguishes discrete from nondiscrete causation, where the latter is suitable to the continuity of cross-temporal causation. I argue, however, that such accounts face conceptual difficulties dating from Zeno’s time. A Bergsonian resolution of these difficulties appears to entail that, for the causal realist, there can be no indirect causal relations of the sort envisioned by Tooley. A consequence of this discussion is that the causal realist must conceive all causal relations as ultimately direct.     

Effect of crack tip sharpness on the strength of vulcanized rubbers

The effect of crack tip sharpness on crack propagation in vulcanized rubbers has been studied. For very sharp cracks, tearing is found to occur on a small scale at very low energies not far above the threshold required for the onset of mechanical crack growth. The “small-scale” tearing energies show relatively little variation for rubbers that differ widely in tear strength as normally measured. Thus the latter property appears to be strongly influenced by variations in the ability of rubbers to promote tip blunting. The small-scale tear behavior is of relevance to other fracture phenomena, including cutting by sharp objects and tensile failure. Natural variations in tip sharpness occur during cyclic or time-dependent mechanical crack growth and influence the form of the crack growth characteristics.     

Nickel peroxide: A more probable intermediate in the Ni(II)‐catalyzed decomposition of peroxomonosulfate

The Ni(II) ion catalyzed thermal decomposition of peroxomonosulfate (PMS) was studied in the pH range 3.42–5.89. The rate is first order in [PMS] and Ni(II) ion concentrations. At pH greater than or equal to 5.23, the reaction becomes zero order in [PMS] and this changeover in the order of the reaction occurs at a higher concentration of nickel ions. The first‐order kinetics in PMS can be explained as a rate‐limiting step and is the transformation of nickel peroxomonosulfate into nickel peroxide. This peroxide intermediate reacts rapidly with another PMS to give oxygen and Ni(II). The formation of nickel peroxide is associated with a small negative or nearly zero entropy of activation. The zero‐order kinetics in [PMS] can be explained by the fact that the hydrolysis of aquated nickel(II) ions into hydroxocompounds is the rate‐limiting step. The turnover number is 2 at pH 3.42 and increases with pH. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 320–237, 2007     

The solution of a convection–diffusion–reaction equation arising from cathodic reduction in a pulsating crack

This paper derives the convection–diffusion-reaction equation governing the reaction between the dissolved oxygen in sea-water and the steel walls of a pulsating crack. By the neglect of the diffusion term it is shown that an exact solution of the convection-reaction equation can be obtained. A numerical method for the solution of the complete convection–diffusion-reaction equation is derived by the use of finite differences. The numerical computation of the initial transient and the final periodic steady-state values is also discussed.     

Inner-sphere oxidation of iron(II) by tris(malonato)cobaltate(III)

The kinetics of oxidation of Fe²⁺ by [Co(C₃H₂O₄)₃]^3? in acidic solutions at 605 nm showed a simple first-order dependence in each reactant concentration. The second-order rate constant dependence on [H⁺] is in accordance with eqn (i) k₂ = k′₂ + k₃[H⁺] (i) where k′₂ and k₃ have values of 73.4 ± 14.0 M ^?1 s^?1 and 353 ± 41 M^?2 s^?1, respectively, at 1.0 M ionic strength (NaClO₄) and 25°C. At 310 nm the formation and decomposition of an intermediate, believed to be [FeC₃H₂O₄]⁺, was observed. The increase in the rate of oxidation with increasing [H⁺] was interpreted in terms of a “one-ended” dissociation mechanism which facilitates chelation of Fe₂₊ by the carbonyl oxygens of malonate in the transition state.     

Relative embeddings of discs into convex domains

Dedicated to the memory of my father