Identifying Local Interfaces.

While interfacial regions often occupy a relatively small portion of a system, physical and chemical processes often proceed differently within them. It is therefore useful to identify interfacial regions to answer many questions in physical chemistry. Thermodynamic phases are often described by their density and local structure; therefore, interfacial regions can then be defined as regions with densities and structures that deviate from the properties of the neighboring phases. Using this perspective of local density and structure around an atom, we describe a "directed search cone" method that has proved useful in identifying atoms that sit at the interface between two regions of a system. We call the set of atoms found to be sitting on the surface "leading atoms", and we construct an interface from these atoms that we call the "leading layer interface". We demonstrate the leading layer interface on solid-vacuum, liquid-vacuum, and liquid-vapor systems. In addition to presenting our method and example calculations, we discuss some observations of local density fluctuations that may be useful for the analysis of heterogeneous systems. Depending on the circumstances, there are various perspectives of an interface that may be insightful, and our leading layer interface will be useful in situations where the correlation between interfacial dynamics and local molecular composition is investigated.

Non-isoplethic measurement on the solid-liquid-vapor equilibrium of binary mixtures at cryogenic temperatures.

We measured the solid-liquid-vapor (SLV) equilibrium of binary mixtures during experiments that alternated between cooling the mixture and injecting the more-volatile component into the sample chamber; thus, the composition of the mixture changed (non-isoplethic) throughout the experiment. Four binary mixtures were used in the experiments to represent mixtures with miscible solid phases (N2/CO) and barely miscible solid solutions (N2/C2H6), as well as mixtures with intermediate solid miscibility (N2/CH4 and CO/CH4). We measured new SLV pressure data for the binary mixtures, except for N2/CH4, which are also available in the literature for verification in this work. While these mixtures are of great interest in planetary science and cryogenics, the resulting pressure data are also needed for modeling purposes. We found the results for N2/CH4 to be consistent with the literature. The resulting new SLV curve for CO/CH4 shows similarities to N2/CH4. Both have two density inversion points (bracketing the temperature range where the solid floats). This result is important for places such as Pluto, Triton, and Titan, where these mixtures exist in vapor, liquid, and solid phases. Based on our experiments, the presence of a eutectic is unlikely for the N2/CH4 and CO/CH4 systems. An azeotrope with or without a peritectic is likely, but further investigations are needed to confirm. The N2/CO system does not have a density inversion point, as the ice always sinks in its liquid. For N2/C2H6, new SLV pressure data were measured near each triple point of the pure components.