Relations between absorption, emission, and excited state chemical potentials from nanocrystal 2D spectra

For quantum-confined nanomaterials, size dispersion causes a static broadening of spectra that has been difficult to measure and invalidates all-optical methods for determining the maximum photovoltage that an excited state can generate. Using femtosecond two-dimensional (2D) spectroscopy to separate size dispersion broadening of absorption and emission spectra allows a test of single-molecule generalized Einstein relations between such spectra for colloidal PbS quantum dots. We show that 2D spectra and these relations determine the thermodynamic standard chemical potential difference between the lowest excited and ground electronic states, which gives the maximum photovoltage. Further, we find that the static line broadening from many slightly different quantum dot structures allows single-molecule generalized Einstein relations to determine the average single-molecule linewidth from Stokes’ frequency shift between ensemble absorption and emission spectra.

Simulation of Vibration Combustion

We consider a mathematical model of the laminar process of vibration combustion proposed recently. It allows us to simulate detonation and deflagration modes, the occurrence of which occurs depending on the structure of the standard chemical potential. For simplicity of presentation and analysis, we consider a one-dimensional mathematical model formulated for the reduced dimensionless variables for the case of a two-component mixture. The obtained numerical results are presented and discussed.

QUESTIONS AND PROBLEMS OF MATHEMATICAL MODELING QUA NONEQUILIBRIUM OF COMBUSTION PROCESSES

On the basis of thermodynamic analysis, new mathematical models of the combus- tion process (thermal theory) and vibrational combustion are constructed. A global inhomo- geneity of the system can be described as an inhomogeneous distribution of the enthalpy over a two-component mixture. In this case, for the combustion process in the phase space of the variables (%, P, T, n, S, E), an increase in the enthalpy is not a total differential. An increase in the enthalpy is a total differential on the local equilibrium manifold (a laminar combustion process). These two assertions, which allow one to single out in the phase space the corre- sponding adiabatic of the combustion process (the Hugoniot adiabatic) and the equation for the entropy, close the classical mathematical model of the combustion process. The above numerical experiments show that two regimes of the combustion process (deflagration and detonation) depend on the structure of the standard chemical potential Moreover, a control of the passive component velocity at the inlet results in (depending on the structure of the standard chemical potential) high-frequency oscillations, which are responsible for a blow-up.

On thermodynamic equilibrium of carbon deposition from gaseous C-H-O mixtures: updating for nanotubes

Extensive literature information on experimental thermodynamic data and theoretical analysis for depositing carbon in various crystallographic forms is examined, and a new three-phase diagram for carbon is proposed. The published methods of quantitative description of gas-solid carbon equilibrium conditions are critically evaluated for filamentous carbon. The standard chemical potential values are accepted only for purified single-walled and multi-walled carbon nanotubes (CNT). Series of C-H-O ternary diagrams are constructed with plots of boundary lines for carbon deposition either as graphite or nanotubes. The lines are computed for nine temperature levels from 200°C to 1000°C and for the total pressure of 1 bar and 10 bar. The diagram for graphite and 1 bar fully conforms to that in (Sasaki K, Teraoka Y. Equilibria in fuel cell gases II. The C-H-O ternary diagrams. J Electrochem Soc 2003b, 150: A885–A888). Allowing for CNTs in carbon deposition leads to significant lowering of the critical carbon content in the reformates in temperatures from 500°C upward with maximum shifting up the deposition boundary O/C values by about 17% and 28%, respectively, at 1 and 10 bar.

Chemico-Physical Causes of Radiation-Induced “Long Cell” Action Corrosion in Water Cooled Reactors

In the previous overview papers [1, 2], the author has identified that ‘long cell action’ corrosion plays a pivotal role in practically all unresolved corrosion issues, irrespective of reactor types and operation. In trying to confirm the existence of radiation-induced ‘long-cell’ action (macro) corrosion cell in the primary cooling system of LWRs, the author attempted to theoretically reproduce the electrochemical potential difference demonstrated during experiments at the INCA Loop in Sweden and the NRI-Rez Loop in the Czech Republic [3, 4]. By performing a radiation chemistry kinetics study combined with electrochemistry calculations, the hydrated electrons, e−aq, reacting mainly with stable molecules, are found to be responsible for inducing a large portion of the potential difference both in the PWR and BWR water chemistry environment. Considering large uncertainties, the author used the standard equilibrium potential as a fitting parameter in the previous studies [3, 4]. The standard chemical potential of the hydrated electron estimated from the fitting parameter is far less than the generally accepted value of 2.86 V. In order to resolve the large discrepancy between the generally accepted values and the estimation from the fitting parameter, the author has developed a ‘mixed’ radiation-electrochemistry formalism, which enables theoretical reconstruction of the observed potential differences more clearly. The previous verifications are updated by using this approach. Through these studies, the author has confirmed the existence of the ‘long cell’ action corrosion mechanism existing in the water-cooled reactors.

Kovats retention index-boiling point relationship of 2-phenyl-2-alkyl-acetonitriles on stationary phases of different polarity

Linear and reciprocial Kovats retention index-boiling point relationships known from the literature were used to study the Kovats retention index-boiling point dependence of 2-phenyl-2-alkylacetonitriles on stationary phases of different polarity (OV-17, OV-210 and OV-225). The standard chemical potential of the partitioning of one methylene group of an n-alkane for the stationary phase was calculated and compared with available literature data.