Chemistry in the Circumstellar Medium: Unveiling the Dust Formation Zone

The growth of dust grains in the inner regions of late-type stars is shrouded in mystery due to the difficulty of understanding the growth of heterogeneous particles from simple atoms and molecules and the lack of observational data. This article reviews the molecular processes important in circumstellar envelopes and discusses how ALMA might be used to probe the dust formation zone either directly or indirectly.

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C(2)mim][NTf2]; the latter behaves as a 'melt' rather than an 'organic solvent'

The electrochemical oxidation of 1-butyl-3-methylimidazolium nitrate [C(4)mim][NO3] was studied by cyclic voltammetry in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [C(2)mim][NTf2]. A sharp peak was observed on a Pt microelectrode (d = 10 mu m), and a diffusion coefficient at infinite dilution of ca. 2.0 x 10(-11) m(2) s(-1) was obtained. Next, the cyclic voltammetry of sodium nitrate (NaNO3) and potassium nitrate (KNO3) was studied, by dissolving small amounts of solid into the RTIL [ C2mim][ NTf2]. Similar oxidation peaks were observed, revealing diffusion coefficients of ca. 8.8 and 9.0 x 10(-12) m(2) s(-1) and solubilities of 11.9 and 10.8 mM for NaNO3 and KNO3, respectively. The smaller diffusion coefficients for NaNO3 and KNO3 (compared to [C(4)mim][NO3]) may indicate that NO3- is ion-paired with Na+ or K+. This work may have applications in the electroanalytical determination of nitrate in RTIL solutions. Furthermore, a reduction feature was observed for both NaNO3 and KNO3, with additional anodic peaks indicating the formation of oxides, peroxides, superoxides and nitrites. This behaviour is surprisingly similar to that obtained from melts of NaNO3 and KNO3 at high temperatures ( ca. 350 - 500 degrees C), and this observation could significantly simplify experimental conditions required to investigate these compounds. We then used X-ray photoelectron spectroscopy (XPS) to suggest that disodium( I) oxide (Na2O), which has found use as a storage compound for hydrogen, was deposited on a Pt electrode surface following the reduction of NaNO3.

Utilization of the three-dimensional volcano surface to understand the chemistry of multiphase systems in heterogeneous catalysis

CO hydrogenation is used as a model system to understand why multiphase catalysts are chemically important in heterogeneous catalysis. By including both adsorption and subsequent surface reactions, kinetic equations are derived with two fundamental properties, the chemisorption energies of C and O (Delta H-C and Delta H-O, respectively). By plotting the activity against Delta H-C and Delta H-O, a 3-D volcano surface is obtained. Because of the constraint between Delta H-C and Delta H-O on monophase systems, a maximum can be achieved. However, if multiphase systems are used, such a constraint can be released and the global maximum may be achieved.

The stereoselective coordination chemistry of the helicating ligand N,N '-bis(-2,2 '-dipyridyl-5-yl)carbonyl-(S/R,S/R)-1,2-diphenylethylenediamine

Enantiomerically pure N,N'-bis(-2,2'-dipyridyl-5-yl)carbonyl-(S/R,S/R)-1,2-diphenylethylenediamine has been synthesised by linking two 2,2'-bipyridine units by (R,R)- and (S,S)-1,2-diphenylethylenediamine. The ligands possess a hindered rotation between the bipyridine chromophores, which are held together by intramolecular hydrogen bonds. ES mass spectroscopy confirmed that reaction with Fe(II), Co(III) and Cd(II) afforded dinuclear complexes. CD spectroscopy implied that enantiopure ligands conferred helicity to the metals centre giving a dominant triple helicate diastereoisomer (with the RR isomer giving a P helicate). H-1 NMR spectroscopy of the cadmium complex confirmed the presence of a single diastereoisomer. (C) 2003 Elsevier B.V. All rights reserved.

Stereoselective coordination chemistry of the tetradentate chelating ligand (2R,3R)-bis(2,2 '-dipyridyl-5-methoxyl) butane

The enantiomerically pure ligand L-3RR (2R, 3R)-bis(2,2'-dipyridyl-5-methoxyl) butane has been synthesised by linking two 2,2'-bipyridine units with (2R, 3R)-butandiol. The reaction of L-3RR with Zn(II) afforded a mononuclear species and the H-1 NMR spectroscopy points to a C-1 symmetry, expected for a distorted trigonal bipyramidal coordination environment. These observations were confirmed by MM2 calculations and electrospray mass spectrometry. The reaction of L-3RR with iron(II) indicated the formation of a dinuclear species by mass spectrometry. Solution state CD spectroscopy indicates that both complexes adopt a Lambda-configuration, implying a single stranded dinuclear iron(II) complex is present rather than the anticipated triple helical architecture.

The Dissociative Recombination of Protonated Acrylonitrile, CH2CHCNH+, with Implications for Nitrile Chemistry in Dark Molecular Clouds and the Upper Atmosphere of Titan

Measurements on the dissociative recombination (DR) of protonated acrylonitrile, CH2CHCNH+, have been performed at the heavy ion storage ring CRYRING located in the Manne Siegbahn Laboratory in Stockholm, Sweden. It has been found that at~2meV relative kinetic energy about 50% of the DR events involve only ruptures of X–H bonds (where X=C or N)while the rest leads to the production of a pair of fragments each containing two heavy atoms (alongside H and/or H2). The absolute DR cross section has been investigated for relative kinetic energies ranging from ~1 meV to 1 eV. The thermal rate coefficient has been determined to follow the expression k(T) = 1.78 × 10-6 (T/300)-0.80 cm3 s-1 for electron temperatures ranging from ~10 to 1000 K. Gas-phase models of the nitrile chemistry in the dark molecular cloud TMC-1 have been run and results are compared with observations. Also, implications of the present results for the nitrile chemistry of Titan’s upper atmosphere are discussed.

The Effects of Molecular Anions on the Chemistry of Dark Clouds

We have investigated the role of molecular anion chemistry in pseudo-time-dependent chemical models of dark clouds. With oxygen-rich elemental abundances, the addition of anions results in a slight improvement in the overall agreement between model results and observations of molecular abundances in Taurus molecular cloud 1 (TMC-1 (CP)). More importantly, with the inclusion of anions, we see an enhanced production efficiency of unsaturated carbon-chain neutral molecules, especially in the longer members of the families C(n)H, C(n)H(2), and HC(n)N. The use of carbon-rich elemental abundances in models of TMC-1 (CP) with anion chemistry worsens the agreement with observations compared with model results obtained in the absence of anions.

Mechanisms and chemistry of dye adsorption on manganese oxides-modified diatomite

The investigations into structural changes which occur during adsorbent modification and the adsorption mechanisms are essential for an effective design of adsorption systems. Manganese oxides were impregnated onto diatomite to form the type known as delta-birnessite. Initial investigations established the effectiveness of manganese oxides-modified diatomite (MOMD) to remove basic and reactive dyes from aqueous solution. The adsorption capacity of MOMD for methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was 320, 419, and 204 mg/g, respectively. Various analytical techniques were used to characterise the structure and the mechanisms of the dye adsorption process onto MOMD such as Fourier transform infrared (FTIR), X-ray diffraction (XRD) and atomic absorption spectrometry (A.A.). A small shift to higher values of the cl-spacing of dye/MOMD was observed indicating that a small amount of the dye molecules were intercalated in the MOMD structure and other molecules were adsorbed on the external surface of MOMD. Two mechanisms of dye adsorption onto MOMD were proposed; intercalation of the dye in the octahedral layers and adsorption of the dye on the MOMD external surface. Moreover, the results demonstrated that the MOMD structure was changed upon insertion of MB and RY with an obvious decrease in the intensity of the second main peak of the MOMD X-ray pattern. (C) 2009 Elsevier Ltd. All rights reserved.