A comparative electrochemical study of diffusion in room temperature ionic liquid solvents versus acetonitrile

Measurements on the diffusion coefficient of the neutral molecule N,N,N',N'-tetramethyl-para-phenylenediamine and the radical cation and dication generated by its one- and two-electron oxidation, respectively, are reported over the range 298-348 K in both acetonitrile and four room temperature ionic liquids (RTILs). Data were collected using single and double potential step chronamperometry at a gold disk electrode of micrometer dimension, and analysed via fitting to the appropriate analytical expression or, where necessary, to simulation. The variation of diffusion coefficient with temperature was found to occur in an Arrhenius-type manner for all combinations of solute and solvent. For a given ionic liquid, the diffusional activation energies of each species were not only closely equivalent to each other, but also to the RTIL's activation energy of viscous flow. In acetonitrile supported with 0.1 M tetrabutylammonium perchlorate, the ratio in diffusion coefficients of the radial cation and dication tot he neutral molecule were calculated as 0.89 +/- 0.05 and 0.51 +/- 0.03, respectively. In contrast, amongst the ionic liquids the same ratios were determined to be on average 0.53 +/- 0.04 and 0.33 +/- 0.03. The consequences of this dissimilarity are considered in terms of the modelling of voltammetric data gathered within ionic liquid solvents.

Double potential step chronoamperometry at microdisk electrodes: simulating the case of unequal diffusion coefficients

An efficient approach to the simulation of the double potential step chronoamperometry at a microdisk electrode based on an exponentially expanding time grid and conformal mapping of the space is presented. The dimensionless second potential step flux data are included as a function of the first potential step duration and the ratio of the diffusion coefficients of the reacting species allowing instant analysis of the experimental double potential step chronoamperograms without a need for simulation. The values of the diffusion coefficients are determined for several test systems and found to be in good agreement with existing literature data. (C) 2004 Elsevier B.V. All rights reserved.

Voltammetry of oxygen in the room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide: One-electron reduction to form superoxide. Steady-state and transient behavior in the same cyclic voltammogram resulting from widely different diffusion coefficients of oxygen and superoxide

The electrochemical reduction of oxygen in two different room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([EMIM][N(Tf)(2)]) and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide ([N-6222][N(Tf)(2)]) was investigated by cyclic voltammetry at a gold microdisk electrode. Chronoamperometric measurements were made to determine the diffusion coefficient, D, and concentration, c, of the electroactive oxygen dissolved in the ionic liquid by fitting experimental transients to the Aoki model. [Aoki, K.; et al. J. Electroanal. Chem. 1981, 122, 19]. A theory and simulation designed for cyclic voltammetry at microdisk electrodes was then employed to determine the diffusion coefficient of the electrogenerated superoxide species, O-2(.-), as well as compute theoretical voltammograms to confirm the values of D and c for neutral oxygen obtained from the transients. As expected, the diffusion coefficient of the superoxide species was found to be smaller than that of the oxygen in both ionic liquids. The diffusion coefficients of O-2 and O-2(.-) in [N-6222][N(Tf)(2)], however, differ by more than a factor of 30 (D-O2 = 1.48 x 10(-10) m(2) s(-1), DO2.- = 4.66 x 10(-12) m(2) s(-1)), whereas they fall within the same order of magnitude in [EMIM][N(Tf)(2)] (D-O2 = 7.3 x 10(-10) m(2) s(-1), DO2.- = 2.7 x 10(-10) m(2) s(-1)). This difference in [N-6222][N(Tf)(2)] causes pronounced asymmetry in the concentration distributions of oxygen and superoxide, resulting in significant differences in the heights of the forward and back peaks in the cyclic voltammograms for the reduction of oxygen. This observation is most likely a result of the higher viscosity of [N-6222][N(Tf)(2)] in comparison to [EMIM][N(Tf)(2)], due to the structural differences in cationic component.

Oxidation of N,N,N ',N '-tetraalkyl-para-phenylenediamines in a series of room temperature ionic liquids incorporating the bis(trifluoromethylsulfonyl)imide anion

The five room temperature ionic liquids: 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([CnMIM][N(Tf)(2)], n = 2, 4, 8, 10) and n-hexyltriethylammonium bis(trifluoromethylsulfonyl)imide ([N-6222][N(Tf)(2)]) were investigated as solvents in which to study the electrochemical oxidation of N,N,N',N'-tetramethyl-para-phenylenediamine (TMPD) and N,N,N',N'-tetrabutyl-paraphenylenediamine (TBPD), using 20 mul micro-samples under vacuum conditions. The effect of dissolved atmospheric gases on the accessible electrochemical window was probed and determined to be less significant than seen previously for ionic liquids containing alternative anions. Chronoamperometric transients recorded at a microdisk electrode were analysed via a process of non-linear curve fitting to yield values for the diffusion coefficients of the electroactive species without requiring a knowledge of their initial concentration. Comparison of experimental and simulated cyclic voltammetry was then employed to corroborate these results and allow diffusion coefficients for the electrogenerated species to be estimated. The diffusion coefficients obtained for the neutral compounds in the five ionic liquids via this analysis were, in units of 10(-11) m(2) s(-1), 2.62, 1.87, 1.12, 1.13 and 0.70 for TMPD. and 1.23, 0.80, 0.40, 0.52 and 0.24 for TBPD (listed using the same order for the ionic liquids as stated above). The most significant consequence of changing the cationic component of the ionic liquid was found to be its effect on the solvent viscosity; the diffusion coefficient of each species was found to be approximately inversely proportional to viscosity across the series of ionic liquids, in accordance with Walden's rule. (C) 2003 Elsevier B.V. All rights reserved.

Full-Scale Marine Exposure Tests on Treated and Untreated Concretes Initial 7-Year Results

An extensive chloride profiling program was undertaken on concrete pier stems erected in the vicinity of the Dornoch Bridge located at the Dornoch Firth in Northeast Scotland. The pier stems were 2 m (6.562 ft) high and octagonal in plan with 0.66 m (2.165 ft) wide faces. The piers were constructed in sets of three with the lowest of each set in the tidal zone and the highest in the atmospheric zone. The pier stems were placed in such a way that they would represent the exposure conditions of the actual bridge piers of the Dornoch Bridge. In all, six of the pier stems were made using plain ordinary portland cement (OPC) concrete (with three of these having the surface treated with silane); the remaining three pier stems had a concrete containing caltite as an additive. Three exposurezones were studied: the tidal zone, the splash zone, and the atmospheric zone. The tidal zone was further subdivided into two levels defined as low-level and high-level. Chloride profiles were obtained from the different regimes over a period of 7 years for all nine pier stems. This paper describes the nature of chloride ingress and the usefulness of diffusion parameters in classifying each exposure regimes. Furthermore, the effectiveness of silane and caltite in protecting concrete from chloride ingress in different exposure zones was studied.

Absolute Atomic Oxygen Density Measurements by Two-Photon Absorption Laser-induced Fluorescence Spectroscopy in an RF-Excited Atmospheric Pressure Plasma Jet

The atmospheric pressure plasma jet is a capacitively coupled radio frequency discharge (13.56 MHz) running with a high helium flux (2m3 h-1) between concentric electrodes. Small amounts (0.5%) of admixed molecular oxygen do not disturb the homogeneous plasma discharge. The jet effluent leaving the discharge through the ring-shaped nozzle contains high concentrations of radicals at a low gas temperature—the key property for a variety of applications aiming at treatment of thermally sensitive surfaces. We report on absolute atomic oxygen density measurements by two-photon absorption laser-induced fluorescence (TALIF) spectroscopy in the jet effluent. Calibration is performed with the aid of a comparative TALIF measurement with xenon. An excitation scheme (different from the one earlier published) providing spectral matching of both the two-photon resonances and the fluorescence transitions is applied.

Absolute Atomic Oxygen Density Distributions in the Effluent of a Micro Scale Atmospheric Pressure Plasma Jet

The coplanar microscale atmospheric pressure plasma jet (µ-APPJ) is a capacitively coupled radio frequency discharge (13.56 MHz, ~15W rf power) designed for optimized optical diagnostic access. It is operated in a homogeneous glow mode with a noble gas flow (1.4 slm He) containing a small admixture of molecular oxygen (~0.5%). Ground state atomic oxygen densities in the effluent up to 2 × 1014 cm-3 are measured by two-photon absorption laser-induced fluorescence spectroscopy (TALIF) providing space resolved density maps. The quantitative calibration of the TALIF setup is performed by comparative measurements with xenon. A maximum of the atomic oxygen density is observed for 0.6% molecular oxygen admixture. Furthermore, an increase in the rf power up to about 15W (depending on gas flow and mixture) leads to an increase in the effluent’s atomic oxygen density, then reaching a constant level for higher powers.

Absolute atomic oxygen density profiles in the discharge core of a microscale atmospheric pressure plasma jet

The micro atmospheric pressure plasma jet is an rf driven (13.56 MHz, ~20 W) capacitively coupled discharge producing a homogeneous plasma at ambient pressure when fed with a gas flow of helium (1.4 slm) containing small admixtures of oxygen (~0.5%). The design provides excellent optical access to the plasma core. Ground state atomic oxygen densities up to 3x1016 cm-3 are measured spatially resolved in the discharge core by absolutely calibrated two-photon absorption laser-induced fluorescence spectroscopy. The atomic oxygen density builds up over the first 8 mm of the discharge channel before saturating at a maximum level. The absolute value increases linearly with applied power.

Generation of Atomic Oxygen in the Effluent of an Atmospheric Pressure Plasma Jet

The planar 13.56MHz RF-excited low temperature atmospheric pressure plasma jet (APPJ) investigated in this study is operated with helium feed gas and a small molecular oxygen admixture. The effluent leaving the discharge through the jet’s nozzle contains very few charged particles and a high reactive oxygen species’ density. As its main reactive radical, essential for numerous applications, the ground state atomic oxygen density in the APPJ’s effluent is measured spatially resolved with two-photon absorption laser induced fluorescence spectroscopy. The atomic oxygen density at the nozzle reaches a value of ~1016 cm-3. Even at several centimetres distance still 1% of this initial atomic oxygen density can be detected. Optical emission spectroscopy (OES) reveals the presence of short living excited oxygen atoms up to 10 cm distance from the jet’s nozzle. The measured high ground state atomic oxygen density and the unaccounted for presence of excited atomic oxygen require further investigations on a possible energy transfer from the APPJ’s discharge region into the effluent: energetic vacuum ultraviolet radiation, measured by OES down to 110 nm, reaches far into the effluent where it is presumed to be responsible for the generation of atomic oxygen.

The dynamics of radio-frequency driven atmospheric pressure plasma jets

The complex dynamics of radio-frequency driven atmospheric pressure plasma jets is investigated using various optical diagnostic techniques and numerical simulations. Absolute number densities of ground state atomic oxygen radicals in the plasma effluent are measured by two-photon absorption laser induced fluorescence spectroscopy (TALIF). Spatial profiles are compared with (vacuum) ultra-violet radiation from excited states of atomic oxygen and molecular oxygen, respectively. The excitation and ionization dynamics in the plasma core are dominated by electron impact and observed by space and phase resolved optical emission spectroscopy (PROES). The electron dynamics is governed through the motion of the plasma boundary sheaths in front of the electrodes as illustrated in numerical simulations using a hybrid code based on fluid equations and kinetic treatment of electrons.

The VLT-FLAMES survey of massive stars: atmospheric parameters and rotational velocity distributions for B-type stars in the Magellanic Clouds (vol 457, pg 265, 2006)

We correct the estimates of the dispersions in the rotational velocities for early-type stars in our Galaxy (Dufton et al. 2006, A&A, 457, 265) and the Magellanic Clouds (Hunter et al. 2008, A&A, 479, 541). The corrected values are pi(1/4) (i.e. approximately 33%) larger than those published in the original papers.

Turbulent diffusion and mixing in interstellar dark clouds with adsorption onto grains

This paper reports the results of models of dark cloud chemistry incorporating a depth dependent density distribution with diffusive mixing and adsorption onto grains. The model is based on the approach taken by Xie et al. (1995), with the addition of grain accretion effects. Without diffusion, the central regions of the cloud freeze out in less than 10(7) years. Freeze-out time is dependent on density, so the diffuse outer region of the cloud remains abundant in gas for about an order of magnitude longer. We find that fairly small amounts of diffusive mixing can delay freeze-out at the centre of the model cloud for a time up to an order of magnitude greater than without diffusion, due to material diffusing inward from the edges of the cloud. The gas-phase lifetime of the cloud core can thus be increased by up to an order of magnitude or more by this process. We have run three different grain models with various diffusion coefficients to investigate the effects of changing the sticking parameters.