Role of proton irradiation and relative air humidity on iron corrosion

This paper presents a study of the effects of proton irradiation on iron corrosion. Since it is known that in humid atmospheres, iron corrosion is enhanced by the double influence of air and humidity, we studied the iron corrosion under irradiation with a 45% relative humidity. Three proton beam intensities (5, 10 and 20 nA) were used. To characterise the corrosion layer, we used ion beam methods (Rutherford Backscattering Spectrometry (RBS), Elastic Recoil Detection Analysis (ERDA)) and X-ray Diffraction (XRD) analysis. The corrosion kinetics are plotted for each proton flux. A diffusion model of the oxidant species is proposed, taking into account the fact that the flux through the surface is dependent on the kinetic factor K. This model provides evidence for the dependence of the diffusion coefficient, D, and the kinetic factor, K, on the proton beam intensity. Comparison of the values for D with the diffusion coefficients for thermal oxygen diffusion in iron at 300 K suggests an enhancement due to irradiation of 6 orders of magnitude

Chemical kinetics in an atmospheric pressure helium plasma containing humidity

Atmospheric pressure plasmas are sources of biologically active oxygen and nitrogen species, which makes them potentially suitable for the use as biomedical devices. Here, experiments and simulations are combined to investigate the formation of the key reactive oxygen species, atomic oxygen (O) and hydroxyl radicals (OH), in a radio-frequency driven atmospheric pressure plasma jet operated in humidified helium. Vacuum ultra-violet high-resolution Fourier-transform absorption spectroscopy and ultra-violet broad-band absorption spectroscopy are used to measure absolute densities of O and OH. These densities increase with increasing H 2 O content in the feed gas, and approach saturation values at higher admixtures on the order of 3 × 10 14 cm −3 for OH and 3 × 10 13 cm −3 for O. Experimental results are used to benchmark densities obtained from zero-dimensional plasma chemical kinetics simulations, which reveal the dominant formation pathways. At low humidity content, O is formed from OH + by proton transfer to H 2 O, which also initiates the formation of large cluster ions. At higher humidity content, O is created by reactions between OH radicals, and lost by recombination with OH. OH is produced mainly from H 2 O + by proton transfer to H 2 O and by electron impact dissociation of H 2 O. It is lost by reactions with other OH molecules to form either H 2 O + O or H 2 O 2 . Formation pathways change as a function of humidity content and position in the plasma channel. The understanding of the chemical kinetics of O and OH gained in this work will help in the development of plasma tailoring strategies to optimise their densities in applications

The Ionic Hydrogen Bond. 5. Polydentate and Solvent-Bridged Structures. Complexing of the Proton and the Hydronium Ion by Polyethers

The thermochemistry associated with protonated complexes containing one or two glyme (MeOCH2CH2-OMe, (G1)), diglyme (Me(OCH2CH2)2OMe, (G2)), or triglyme (Me(OCH2CH2)3OMe (G3)) molecules and 0-3 H2O molecules was measured by pulsed high-pressure mass spectrometry. Comparison of polyether, crown ether, and acetone complexes with H+ and H3O+ shows increasing binding energies with increasing flexibility in the ligands. For example, in protonated clusters containing ligands with a total of four polar groups, the proton is bonded by a total energy of (kJ/mol (kcal/mol)): four Me2CO molecules, 1044.8 (249.7); two G1 molecules, 987.4 (236.0); one G3 molecule, 962.3 (230.0); 12-crown-4, 941.4 (225.0). Stabilization of the proton by dipoles of the free ether groups contributes significantly; for example, 17 and 54 kJ/mol (4 and 13 kcal/mol) in the binding energy within (G1)2H+ and (G2)2H+ dimers, respectively. The thermochemistry of HaO+ binding indicates bidentate complexes with one each of G2, G3, and 15-crown-5 molecules and two G1 molecules, with binding energies of 310-352 kJ/mol (74-84 kcal/mol). In these complexes the second OH+.O bond contributes up to 1 13 kJ/mol(27 kcal/mol). Larger binding energies of 387-475 kJ/mol (93-99 kcal/mol) indicate tridentate complexes of H3O+ with two G1 and two G3 molecules, as well as with 18-crown-6, which is the best complexing agent due to entropy effects. In complexes containing additional water molecules, the thermochemistry suggests that two H2O molecules form a protonated solvent bridge between ether groups in (G1.2H2O)H+ and (G3.2H2O)H+. Ab initio calculations show that open and solvent-bridged structures have comparable energies (within 16 kJ/mol(4 kcal/mol)). The calculated barriers to direct and solvent-mediated proton transfer between functional groups are 0-16 kJ/mol (04 kcal/mol). The solvent-bridged structures are models for water chains involved in proton transport in biomembranes

Isotope exchange in ionized CO2/CO mixtures: the role of asymmetrical C2O3+ ions

A hitherto unknown, atmospherically relevant, isotope-exchange reaction was studied in ionised gaseous mixtures containing carbon dioxide and monoxide. The mechanism of the O exchange, proceeding over a double-minimum potential-energy surface, was positively established by mass spectrometric and theoretical methods that also allowed the identification and characterisation of the C2O3+ intermediate. The increase of internal energy displaces the observed reactivity towards an endothermic reaction path that involves only CO2 and represents an indirect route to the dissociation of carbon dioxide