LD2668 .T4 1966 W891 / Master of Science

published_or_final_version / Mechanical Engineering / Master / Master of Science in Engineering

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Many well-known arguments in the philosophy of mind use thought experiments to elicit intuitions about consciousness. Often, these thought experiments include mechanistic explanations of a systems’ behavior. I argue that when we understand a system as a mechanism, we are not likely to understand it as an agent. According to Arico, Fiala, Goldberg, and Nichols’ (2011) AGENCY Model, understanding a system as an agent is necessary for generating the intuition that it is conscious. Thus, if we are presented with a mechanistic description of a system, we will be very unlikely to understand that system as conscious. Many of the thought experiments in the philosophy of mind describe systems mechanistically. I argue that my account of consciousness attributions is preferable to the “Simplicity Intuition” account proposed by David Barnett (2008) because it is more explanatory and more consistent with our intuitions. Still, the same conclusion follows from Barnett’s “Simplicity” account and from my own account: we should reassess the conclusions that have been drawn from many famous thought experiments.

Spectral and kinetic studies made on CoPc over a concentration range of 1.72 x 10-6M – 1.00 x 10-5M in DMSO are consistent with a monomer-dimer equilibrium at 303 K. The dimerization constant obtained at 303 K is 1.67 x 104M-1 and is two to three orders of magnitude smaller than those of several tetrasulfonated metallophthalocyanines in aqueous solution. The rate constants for the formation and dissociation of the CoPc dimer in DMSO at 303 K are 1.29 x 102M-1s-1 and 7.20 x 10-3s-1, respectively. The low dimerization constant for CoPc in DMSO is attributed to its relatively slow rate of dimer formation. Introduction of cyanide, detergents, and salts to solutions of CoPc in DMSO all enhanced the dissociation of the CoPc dimer. Furthermore, both cyanide and the catonic detergent cetyl trimethylammonium bromide (CTAB) at concentrations of 6.0 x 10-2M and higher, facilitate oxidation of cobalt in CoPc. For cyanide, this is accomplished by destabilization of the metal eg electrons by back-bonding in the axial positions of CoPc while the CTAB detergent forms a micelle which encapsulates a CoPc monomer striping the dye of axial DMSO molecules in the process. Thus, oxygen can bind to the vacant axial positions on the metal. Kinetic studies of the interactions between cyanide and CoPc in DMSO show two fast reactions which are attributed to the addition of cyanide to the axial positions of CoPc. The rate constants for the addition of the first and second cyanide ligands to CoPc are 7.72 x 105M-1s-1 and 5.51 x 104M-1s-1, respectively, at 299 K. Activation parameters, ΔHs* and ΔSs* for the second cyanide addition are 9.9 kcal/mol and -4.0 e.u., respectively. Both additions are faster than the corresponding reactions with CoTSPc4- in DMSO. The three detergents sodium dodecyl sulfate (SDS), Triton X-100, and cetyl trimethylammonium bromide (CTAB) dissociate the CoPc dimer more than by dilution with DMSO. Furthermore, Triton X-100 dissociates the CoPc dimer at about the same rate as CTAB while SDS is not as efficient at comparable concentrations to CTAB. The critical micelle concentration for the CTAB-DMSO system is reached at a CTAB concentration of 6.0 x 10-2M where the CoPc dimer dissociation rate nearly triples compared to solvent dilution and oxidation of the metal in CoPc is observed. The addition of tetraethylammonium bromide, tetrapropylammonium bromide and tetrabutylammonium bromide to CoPc in DMSO increases the dimer dissociation rate by a factor of two compared to dilution with DMSO. All salts dissociate the CoPc dimer at similar rates suggesting the hydrocarbon chain is of insufficient length to be as effective as CTAB. Finally, oxygen does not seem to effect the dissociation of the CoPc dimer in DMSO

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The elastic constants, phase stability, heat of formation and the Debye temperature of various noble metal compounds in the stoichiometry A3B (where A = Pt, Ir, Rh, Ru, Pd and B = Al, Hf, Zr, Sc) were studied using the ab initio Density Functional Theory - Projector Augmented Wave method. A total of 24 compositions was investigated, of which 16 compounds were predicted to be thermodynamically stable. The remaining eight compounds were found not energetically favorable, due to positive or low heats of formation. According to the Density of States studies, the L12 structure was predicted in 8 compounds while four compounds had the D024 structure. Among compounds with the L12 structure, the hardest phase predicted was L12-Ir3Hf. L12-Pd3Sc was predicted as the least hard and most ductile compound. In compounds with the D024 structure, Pt3Zr was predicted having highest hardness and highest melting point. In all the compounds, the strongest interaction was found between hafnium and the noble metals and least interaction was with aluminum. The melting points from ab initio and molecular dynamics calculations slightly over-predicted experimental values, but showed the same trends. Both the fracture toughnesses and the melting points deduced using the Sutton-Chen potentials had similar trends to ab initio results, suggesting that the Sutton-Chen potentials is adequate for simulating metallic phases.