RESUMO
The influence of oxygen on liquid-gas surface tension of molten metals has been well-investigated experimentally and modeled theoretically via the Szyszkowski equation, derivable from the Butler molecular monolayer interface model. However, there is no corresponding model describing the experimentally observed profound effect of oxygen partial pressure on solid-liquid surface tension as well as on contact angle of molten metals on ceramic substrates. Here, we utilize the Butler-Sugimoto thermodynamic approach based on a monomolecular bilayer interface model to investigate the effect of oxygen partial pressure on liquid-gas as well as solid-liquid surface tension of molten Cu/Al2O3 and molten Ag/Al2O3 systems. It is shown that both liquid-gas and solid-liquid surface tension are a strong function of oxygen activity in the melt, which, in turn, depends on gas-phase oxygen partial pressure, in conformity with experiments. The change in solid-liquid surface tension and wetting is also greatly affected by the change in liquid-gas surface tension. This improved understanding is of practical significance in many applications.
RESUMO
The concept of reaction route (RR) graphs introduced recently by us for kinetic mechanisms that produce minimal graphs is extended to the problem of non-minimal kinetic mechanisms for the case of a single overall reaction (OR). A RR graph is said to be minimal if all of the stoichiometric numbers in all direct RRs of the mechanism are equal to +/-1 and non-minimal if at least one stoichiometric number in a direct RR is non-unity, e.g., equal to +/-2. For a given mechanism, four unique topological characteristics of RR graphs are defined and enumerated, namely, direct full routes (FRs), empty routes (ERs), intermediate nodes (INs), and terminal nodes (TNs). These are further utilized to construct the RR graphs. One algorithm involves viewing each IN as a central node in a RR sub-graph. As a result, the construction and enumeration of RR graphs are reduced to the problem of balancing the peripheral nodes in the RR sub-graphs according to the list of FRs, ERs, INs, and TNs. An alternate method involves using an independent set of RRs to draw the RR graph while satisfying the INs and TNs. Three examples are presented to illustrate the application of non-minimal RR graph theory.
RESUMO
An unusual analogy between the quantitative structure-property relationships (QSPR), stoichiometry, chemical thermodynamics, and kinetics is presented. Namely, the conventional ordinary least-squares (OLS) QSPR analysis is modified so as to explicitly minimize the residuals of the species subject to a set of linear relations among the residuals. The ways the linear relations among the residuals are visualized and defined totally resemble the formalism of chemical stoichiometry and, therefore, were called isostructural reactions. It is further proved that the residuals may be uniquely partitioned into a sum of contributions associated with a set of isostructural reactions that have the same properties as the response reactions (RERs) previously deduced by us from chemical thermodynamics and kinetics. This finding is shown to be a useful tool for a deeper understanding of the QSPR. In particular, the isostructural RERs approach may be effectively used to detect the outliers.
