Extraction of electrode kinetic parameters from microdisc voltammetric data measured under transport conditions intermediate between steady-state convergent and transient linear diffusion as typically applies to room temperature ionic liquids

The extraction of electrode kinetic parameters for electrochemical couples in room-temperature ionic liquids (RTILs) is currently an area of considerable interest. Electrochemists typically measure electrode kinetics in the limits of either transient planar or steady-state convergent diffusion for which the voltammetic response is well understood. In this paper we develop a general method allowing the extraction of this kinetic data in the region where the diffusion is intermediate between the planar and convergent limits, such as is often encountered in RTILs using microelectrode voltammetry. A general working surface is derived, allowing the inference of Butler-Volmer standard electrochemical rate constants for the peak-to-peak potential separation in a cyclic voltammogram as a function of voltage scan rate. The method is applied to the case of the ferrocene/ferrocenium couple in [C(2)mim][N(Tf)(2)] and [C(4)mim][N(Tf)(2)].

Oxidation of several p-phenylenediamines in room temperature ionic liquids: Estimation of transport and electrode kinetic parameters

The electrochemical oxidation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) has been studied by cyclic voltammetry and potential step chronoamperometry at 303 K in five ionic liquids, namely [C(2)mim] [NTf2], [C(4)mim] [NTf2] [C(4)mpyrr] [NTf2] [C(4)mim] [BF4], and [C(4)mim] [PF6] (where [C(n)mim](+) = 1-alkyl-3-methylimidazolium, [C(4)mpyrr](+) = N-butyl-N-methylpyrrolidinium, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [BF4](-) = tetrafluoroborate, and [PF6](-) = hexafluorophosphate). Diffusion coefficients, D, of 4.87, 3.32, 2.05, 1.74, and 1.34 x 10(-11) m(2) s(-1) and heterogeneous electron-transfer rate constants, k(0), of 0.0109, 0.0103, 0.0079, 0.0066, and 0.0059 cm s(-1) were calculated for TMPD in [C(2)mim] [NTf2], [C(4)mim] [NTf2], [C(4)mpyrr] [NTf2], [C(4)mim] [BF4], and [C(4)mim] [PF6], respectively, at 303 K. The oxidation of TMPD in [C4mim][PF6] was also carried out at increasing temperatures from 303 to 343 K, with an activation energy for diffusion of 32.3 kJ mol(-1). k(0) was found to increase systematically with increasing temperature, and an activation energy of 31.4 kJ mol(-1) was calculated. The study was extended to six other p-phenylenediamines with alkyl/phenyl group substitutions. D and k(0) values were calculated for these compounds in [C(2)mim] [NTf2], and it was found that k(0) showed no obvious relationship with the hydrodynamic radius, r.

Measurements of absolute, single charge-exchange cross sections of H+, He+ and He2+ with H2O and CO2

Absolute measurements have been made of single-electron charge-exchange cross sections of H+, He+, and He2+ in H2O and CO2 in the energy range 0.3-7.5 keV amu(-1). Collisions of this type occur in the interaction of solar wind ions with cometary gases and have been observed by the Giotto spacecraft using the Ion Mass Spectrometer/High Energy Range Spectrometer (IMS/HERS) during a close encounter with comet Halley in 1986. Increases in the He+ ion density, and in the He2+ to H+ density ratio were reported by Shelley et al, and Fuselier et al. and were explained by charge exchange. However, the lack of reliable cross sections for this process made interpretation of the data difficult. New cross sections are presented and discussed in relation to the Giotto observations.

Transport Properties of Self-Consolidating Concrete

The permeability of concrete is influenced by the porosity and the interconnectivity of the pores in the cement paste and the microcracks in concrete, especially in the interface of paste-aggregate. The movements of gases, liquids, and ions through concrete is important because of their interactions with concrete constituents, including pore water, which can alter the integrity of concrete directly and indirectly, leading to the deterioration of structures. This study reports the findings from an investigation carried out to study the effect of the mixture variations on the durability of medium- and high-strength self-consolidating concrete (SCC). The mixture variations studied include the type of mineral admixtures, such as limestone powder (LSP) and pulverized fuel ash (PFA), and viscositymodifying admixtures (VMA) for both medium- and high-strength SCC. Air permeability, water permeability, capillary absorption, and chloride diffusivity were used to assess the durability of SCC mixtures in comparison with normal, vibrated concretes. The results showed that SCC mixtures, for medium- and high-strength grades using PFA followed by LSP, have lower permeability properties compared with normal concretes. SCC made with VMA had a higher sorptivity, air permeability, and water permeability compared with other SCC mixtures, which can be attributed to higher watercement ratio (w/c) and lack of pore filling effect. An in-place migration coefficient was obtained using the in-place ion migration test. This was used to compare the potential diffusivity of different concretes. The results indicated that SCC, for both grades of strength, made with PFA showed much lower diffusivity values in comparison with other mixtures, whereas the SCC mixtures with VMA showed higher diffusivity.

Nonisothermal moisture transport in hygroscopic building materials: modeling for the determination of moisture transport coefficients

A mathematical model for calculating the nonisothermal moisture transfer in building materials is presented in the article. The coupled heat and moisture transfer problem was modeled. Vapor content and temperature were chosen as principal driving potentials. The coupled equations were solved by an analytical method, which consists of applying the Laplace transform technique and the Transfer Function Method. A new experimental methodology for determining the temperature gradient coefficient for building materials was also proposed. Both the moisture diffusion coefficient and the temperature gradient coefficient for building material were experimentally evaluated. Using the measured moisture transport coefficients, the temperature and vapor content distribution inside building materials were predicted by the new model. The results were compared with experimental data. A good agreement was obtained.

Inelastic quantum transport in nanostructures: The self-consistent Born approximation and correlated electron-ion dynamics

A dynamical method for inelastic transport simulations in nanostructures is compared to a steady-state method based on nonequilibrium Green's functions. A simplified form of the dynamical method produces, in the steady state in the weak-coupling limit, effective self-energies analogous to those in the Born approximation due to electron-phonon coupling. The two methods are then compared numerically on a resonant system consisting of a linear trimer weakly embedded between metal electrodes. This system exhibits an enhanced heating at high biases and long phonon equilibration times. Despite the differences in their formulation, the static and dynamical methods capture local current-induced heating and inelastic corrections to the current with good agreement over a wide range of conditions, except in the limit of very high vibrational excitations where differences begin to emerge.