Variations Of Chemical Species Research Articles

Thermodynamic and stoichiometric laws ruling the fates of growing systems

We delve into growing open chemical reaction systems (CRSs) characterized by autocatalytic reactions within a variable volume, which changes in response to these reactions. Understanding the thermodynamics of such systems is crucial for comprehending biological cells and constructing protocells because it sheds light on the physical conditions necessary for their self-replication. Building on our recent work, where we developed a thermodynamic theory for growing CRSs featuring basic autocatalytic motifs with regular stoichiometric matrices, we now expand this theory to include scenarios where the stoichiometric matrix has a nontrivial left kernel space. This extension introduces conservation laws, which limit the variations in chemical species due to reactions, thereby confining the system's possible states to those compatible with its initial conditions. By considering both thermodynamic and stoichiometric constraints, we clarify the environmental and initial conditions that dictate the CRSs' fate—whether they grow, shrink, or reach equilibrium. We also find that the conserved quantities significantly influence the equilibrium state achieved by a growing CRS. These results are derived independently of specific thermodynamic potentials or reaction kinetics, therefore underscoring the fundamental impact of conservation laws on the growth of the system. Published by the American Physical Society 2024

Detailed Kinetic Model for the Thermal Decomposition of Hydrazine Nitrate in Nitric Acid Solution Based on Quantum Chemistry Calculations Combined with the Polarizable Continuum Model.

The decomposition mechanism of hydrazine nitrate in nitric acid solutions was investigated using quantum chemistry calculations combined with the polarizable continuum model at the CBS-QB3//ωB97X-D/SMD level of theory. These calculations provided a detailed kinetic model incorporating rate coefficients and thermodynamic data. Rate coefficients were determined using traditional transition state theory, while diffusion-limited reactions were modeled based on the Einstein-Stokes equations. The resulting model comprised the kinetics for 108 reactions and thermodynamic data for 58 species. This model was validated by comparing simulations of the variations in chemical species during the decomposition process to experimental data acquired under isothermal conditions at 100 °C. The model was found to accurately reproduce the concentration changes of N2H4, HN3, and NH3 and also explained the reaction mechanism. The thermal decomposition was found to proceed via two parallel paths: N2H4 + HNO3 → H2O + HONO + N2H2 and N2H4 + HONO → HN3 + 2H2O. Following these reactions, a portion of the HN3 decomposes to produce NH3 through a multistep process. A sensitivity analysis showed that the rate of decomposition is greatly affected by the pH of the solution.

Distinctive oil shale pyrolysis behavior in indirectly heated fixed bed with internals

Variation of chemical species from pyrolysis with temperature, with light oil/diesel and VGO dominant at temperatures below 450 °C and above 300 °C.

Numerical study on combustion of H2—O2 in a supersonic reactive expansion in a nozzle

A study on expansion flow inside a nozzle considering full mechanism chemistry of hydrogen and oxygen was carried out. In this study, a full implicit scheme for turbulent reactive flow was obtained by combining the second order TVD scheme of Yee and Harten (1987, Implicit TVD schemes for hyperbolic conservation laws in curvilinear coordinates. American Institute of Aeronautics and Astronautics Journal, 25(2), 266–274) with the efficient implicit lower-upper scheme of Shuen and Yoon (1989, Numerical study of chemically reacting flows using a lower-upper symmetric successive overrelaxation scheme. American Institute of Aeronautics and Astronautics Journal, 27(12), 1752–1756). The species equations, Navier–Stokes equations and turbulence model were implemented in the numerical scheme and solved in conjunction with full detailed finite rate chemistry. The numerical scheme is verified by comparison with experimental results of a converging–diverging nozzle. Effects of inlet pressure, temperature and fuel-oxidant mass ratio on nozzle flow field were studied. Variation of chemical species under different conditions was investigated by considering a chemical mechanism. Results show that increasing inlet pressure increases the rate of reactions due to increasing the concentration of reactants. For lower inlet pressure the radical H increases slightly in the diverging part of the nozzle, while for higher pressures it decreases along the nozzle. Inlet fuel–oxidant mass ratio affects the variation of all species with a greater effect for a near stoichiometric ratio. It was also shown that a higher inlet temperature provides a more enhanced reaction zone in the diverging part of the nozzle.

Aerosol and Precipitation Chemistry during the Summer at the Summit of Mt. Fuji, Japan (3776m a.s.l.)

Aerosol and precipitation samples were obtained at the summit of Mt. Fuji, the highest peak (3776m a.s.l.) in Japan, in the summers of 1997, 1998, and 1999. The mountaintop might be affected by valley wind during the afternoon, but is located in the free troposphere during the morning. The temporal variations of chemical species in the aerosol and precipitation samples correspond with meteorological conditions. The SO4 2− in the aerosol and precipitation exhibits high concentration with low temperature air mass, indicating the influence of long range transport from the Asian Continent. The contribution of the free troposphere to the chemical species obtained at the summit is estimated to be at least 30% during the summer season.