The Evolution of Multicomponent Systems at High Pressures: VI. The Thermodynamic Stability of the Hydrogen-Carbon System: The Genesis of Hydrocarbons and the Origin of Petroleum

The spontaneous genesis of hydrocarbons which comprise natural petroleum have been analyzed by chemical thermodynamic stability theory. The constraints imposed upon chemical evolution by the second law of thermodynamics are briefly reviewed; and the effective prohibition of transformation, in the regime of temperatures and pressures characteristic of the near-surface crust of the Earth, of biological molecules into hydrocarbon molecules heavier than methane is recognized. A general, first-principles equation of state has been developed by extending scaled particle theory (SPT) and by using the technique of the factored partition function of the Simplified Perturbed Hard Chain Theory (SPHCT). The chemical potentials, and the respective thermodynamic Affinity, have been calculated for typical components of the hydrogen-carbon (H-C) system over a range pressures between 1-100 kbar, and at temperatures consistent with those of the depths of the Earth at such pressures. The theoretical analyses establish that the normal alkanes, the homologous hydrocarbon group of lowest chemical potential, evolve only at pressures greater than approximately thirty kbar, excepting only the lightest, methane. The pressure of thirty kbar corresponds to depths of approximately 100 km. Special high-pressure apparatus has been designed which permits investigations at pressures to 50 kbar and temperatures to 2000 K, and which also allows rapid cooling while maintaining high pressures. The high-pressure genesis of petroleum hydrocarbons has been demonstrated using only the solid reagents iron oxide, FeO, and marble, CaCO3, 99.9% pure and wet with triple-distilled water

Search for cold and hot gas in the ram pressure stripped Virgo dwarf galaxy IC3418

We present IRAM 30m sensitive upper limits on CO emission in the ram pressure stripped dwarf Virgo galaxy IC3418 and in a few positions covering HII regions in its prominent 17 kpc UV/Ha gas-stripped tail. In the central few arcseconds of the galaxy, we report a possible marginal detection of about 1x10^6 M_sun of molecular gas (assuming a Galactic CO-to-H_2 conversion factor) that could correspond to a surviving nuclear gas reservoir. We estimate that there is less molecular gas in the main body of IC3418, by at least a factor of 20, than would be expected from the pre-quenching UV-based star formation rate assuming the typical gas depletion timescale of 2 Gyr. Given the lack of star formation in the main body, we think the H_2-deficiency is real, although some of it may also arise from a higher CO-to-H_2 factor typical in low-metallicity, low-mass galaxies. The presence of HII regions in the tail of IC3418 suggests that there must be some dense gas; however, only upper limits of < 1x10^6 M_sun were found in the three observed points in the outer tail. This yields an upper limit on the molecular gas content of the whole tail < 1x10^7 M_sun, which is an amount similar to the estimates from the observed star formation rate over the tail. We also present strong upper limits on the X-ray emission of the stripped gas in IC3418 from a new Chandra observation. The measured X-ray luminosity of the IC3418 tail is about 280 times lower than that of ESO 137-001, a spiral galaxy in a more distant cluster with a prominent ram pressure stripped tail. Non-detection of any diffuse X-ray emission in the IC3418 tail may be due to a low gas content in the tail associated with its advanced evolutionary state and/or due to a rather low thermal pressure of the surrounding intra-cluster medium.Comment: 15 pages, 11 figures, A&A accepte

Random sequential adsorption of shrinking or spreading particles

We present a model of one-dimensional irreversible adsorption in which particles once adsorbed immediately shrink to a smaller size or expand to a larger size. Exact solutions for the fill factor and the particle number variance as a function of the size change are obtained. Results are compared with approximate analytical solutions.Comment: 9 pages, 8 figure

Magnetic field configuration associated with solar gamma ray flares in June, 1991

The vector magnetic field configuration of the solar active region AR 6659 that produced very high levels of flare activity in Jun. 1991 is described. The morphology and evolution of the photospheric fields are described for the period 7-10 Jun., and the flares taking place around these dates and their locations relative to the photospheric fields are indicated. By comparing the observed vector field with the potential field calculated from the observed line-of-sight flux, we identify the nonpotential characteristics of the fields along the magnetic neutral lines where the flares were observed. These results are compared with those from the earlier study of gamma-ray flares

The microcanonical thermodynamics of finite systems: The microscopic origin of condensation and phase separations; and the conditions for heat flow from lower to higher temperatures

Microcanonical thermodynamics allows the application of statistical mechanics both to finite and even small systems and also to the largest, self-gravitating ones. However, one must reconsider the fundamental principles of statistical mechanics especially its key quantity, entropy. Whereas in conventional thermostatistics, the homogeneity and extensivity of the system and the concavity of its entropy are central conditions, these fail for the systems considered here. For example, at phase separation, the entropy, S(E), is necessarily convex to make exp[S(E)-E/T] bimodal in E. Particularly, as inhomogeneities and surface effects cannot be scaled away, one must be careful with the standard arguments of splitting a system into two subsystems, or bringing two systems into thermal contact with energy or particle exchange. Not only the volume part of the entropy must be considered. As will be shown here, when removing constraints in regions of a negative heat capacity, the system may even relax under a flow of heat (energy) against a temperature slope. Thus the Clausius formulation of the second law: ``Heat always flows from hot to cold'', can be violated. Temperature is not a necessary or fundamental control parameter of thermostatistics. However, the second law is still satisfied and the total Boltzmann entropy increases. In the final sections of this paper, the general microscopic mechanism leading to condensation and to the convexity of the microcanonical entropy at phase separation is sketched. Also the microscopic conditions for the existence (or non-existence) of a critical end-point of the phase-separation are discussed. This is explained for the liquid-gas and the solid-liquid transition.Comment: 23 pages, 2 figures, Accepted for publication in the Journal of Chemical Physic

Scattering a pulse from a chaotic cavity: Transitioning from algebraic to exponential decay

The ensemble averaged power scattered in and out of lossless chaotic cavities decays as a power law in time for large times. In the case of a pulse with a finite duration, the power scattered from a single realization of a cavity closely tracks the power law ensemble decay initially, but eventually transitions to an exponential decay. In this paper, we explore the nature of this transition in the case of coupling to a single port. We find that for a given pulse shape, the properties of the transition are universal if time is properly normalized. We define the crossover time to be the time at which the deviations from the mean of the reflected power in individual realizations become comparable to the mean reflected power. We demonstrate numerically that, for randomly chosen cavity realizations and given pulse shapes, the probability distribution function of reflected power depends only on time, normalized to this crossover time.Comment: 23 pages, 5 figure