Solvation of O(2)(-) and O(4)(-) by p-difluorobenzene and p-xylene studied by photoelectron spectroscopy

Anion photoelectron spectra of the O(2)(-) . arene and O(4)(-) . arene complexes with p-xylene and p-difluorobenzene are presented and analyzed with the aid of calculations on the anions and corresponding neutrals. Relative to the adiabatic electron affinity of O(2), the O(2)(-) . arene spectra are blueshifted by 0.75-1 eV. Solvation energy alone does not account for this shift, and it is proposed that a repulsive portion of the neutral potential energy surface is accessed in the detachment, resulting in dissociative photodetachment. O(2)(-) is found to interact more strongly with the p-difluorobenzene than the p-xylene. The binding motif involves the O(2)(-) in plane with the arene, interacting via electron donation along nearby C-H bonds. A peak found at 4.36(2) eV in the photoelectron spectrum of O(2)(-) . p-difluorobenzene (p-DFB) is tentatively attributed to the charge transfer state, O(2)(-) . p-DFB(+). Spectra of O(4)(-) . arene complexes show less blueshift in electron binding energy relative to the spectrum of bare O(4)(-), which itself undergoes dissociative photodetachment. The striking similarity between the profiles of the O(4)(-) . arene complexes with the O(4)(-) spectrum suggests that the O(4)(-) molecule remains intact upon complex formation, and delocalization of the charge across the O(4)(-) molecule results in similar structures for the anion and neutral complexes.     

Addition of NH3 to Al3O3-

Recent computational studies on the addition of ammonia (NH3) to the Al3O3- cluster anion [A. Guevara-Garcia, A. Martinez, and J. V. Ortiz, J. Chem. Phys. 122, 214309 (2005)] have motivated experimental and additional computational studies, reported here. Al3O3- is observed to react with a single NH3 molecule to form the Al3O3NH3- ion in mass spectrometric studies. This is in contrast to similarly performed studies with water, in which the Al3O5H4- product was highly favored. However, the anion PE spectrum of the ammoniated species is very similar to that of Al3O4H2-. The adiabatic electron affinity of Al3O3NH3 is determined to be 2.35(5) eV. Based on comparison between the spectra and calculated electron affinities, it appears that NH3 adds dissociatively to Al3O3-, suggesting that the time for the Al3O3-NH3 complex to either overcome or tunnel through the barrier to proton transfer (which is higher for NH3 than for water) is short relative to the time for collisional cooling in the experiment.     

Tensammetric determination of non-ionic surfactants combined with BiAS separation procedure (Wickbold) 2. Optimisation of the precipitation and investigation of interferences

The precipitation step in the developed procedure (BiAS-ITM) was optimised with the aim of achieving a lower detection limit. Losses during filtration using Triton X-100 as representative non-ionic surfactant (NS), the indirect tensammetric method (ITM) and adsorptive stripping tensammetry (AdST) for the determination of the concentration of the surfactant in the precipitate and in the filtrate were investigated. The G4 glass filter recommended up to now was found to be insufficiently effective and a source of loss. The new version of the procedure developed works within the range 2-1000 mug of NS in the sample, and thus two orders of magnitude lower than the former version of the procedure, showing satisfactory recovery and precision. The detection limit (3 x S.D.) was found to be below 1.5 mug in the sample. Interferences of anionic surfactants (ASs) e.g. sodium dodecylbenzenesulphonate and sodium lauryl sulphate, lipids, e.g. glycerol trioleate (GTO), and chlorophyll were investigated. GTO and AS show no effect on the BiAS-ITM results although strong adsorption of ASs on the glass filter as well as a slight adsorption on the precipitate was found. Chlorophyll does not interfere with the determination up to 30 mug in the sample, whereas higher concentrations produce results that are too high.