Group additive values for the gas phase standard enthalpy of formation of hydrocarbons and hydrocarbon radicals

A complete and consistent set of 95 Benson group additive values (GAV) for the standard enthalpy of formation of hydrocarbons and hydrocarbon radicals at 298 K and 1 bar is derived from an extensive and accurate database of 233 ab initio standard enthalpies of formation, calculated at the CBS-QB3 level of theory. The accuracy of the database was further improved by adding newly determined bond additive corrections (BAC) to the CBS-QB3 enthalpies. The mean absolute deviation (MAD) for a training set of 51 hydrocarbons is better than 2 kJ mol(-1). GAVs for 16 hydrocarbon groups, i.e., C(C(d))(3)(C), C-(C(d))(4), C-(C(t))(C(d))(C)(2), C-(C(t))(C(d))(2)(C), C-(C(t))(C(d))(3), C-(C(t))(2)(C)(2), C-(C(t))(2)(C(d))(C), C-(C(t))(2)(C(d))(2), C-(C(t))(3)(C), C-(C(t))(3)(C(d)), C-(C(t))(4), C-(C(b))(C(d))(C)(H), C-(C(b))(C(t))(H)(2), C-(C(b))(C(t))(C)(H), C-(C(b))(C(t))(C)(2), C(d)-(C(b))(C(t)), for 25 hydrocarbon radical groups, and several ring strain corrections (RSC) are determined for the first time. The new parameters significantly extend the applicability of Benson's group additivity method. The extensive database allowed an evaluation of previously proposed methods to account for non-next-nearest neighbor interactions (NNI). Here, a novel consistent scheme is proposed to account for NNIs in radicals. In addition, hydrogen bond increments (HBI) are determined for the calculation of radical standard enthalpies of formation. In particular for resonance stabilized radicals, the HBI method provides an improvement over Benson's group additivity method.     

Accreditation of reference material producers: the example of IRMM's Reference Materials Unit

The potential approaches for third-party assessment of reference material producers are revisited and the activities of the Reference Materials (RM) Unit of the Institute for Reference Materials and Measurements (IRMM) to obtain accreditation to ISO Guide 34 and ISO 17025 are described. Accreditation was related to the Unit as all matrix RM activities of the institute are concentrated there. A management system was established that allows sufficient flexibility to be applicable to a wide range of RMs while being precise enough to ensure compliance with ISO Guides 30, 31 and especially 34 and 35. Accreditation was achieved in 2004 with independent scopes for testing and RM production and was confirmed and extended in 2005. The key aspects of the RM Unit's management system for RM production are presented. Presented at BERM-10, April 2006, Charleston, SC, USA     

Enhanced fluorescence from o-phthalaldehyde and fluorescamine fluorophores using Triton and β-cyclodextrin

Mexiletine— and lysine hydrochloride—o-phthalaldehyde and mexiletine hydrochloride—, cysteine—, cysteamine—, homocysteine— and lysine hydrochloride—fluorescamine derivatives were subjected to Triton and β-cyclodextrin enhancement treatments. Of several classical fluorescence-enhancing reagents tested (Triton, β-cyclodextrin, sodium dodecyl sulphate, Brij), Triton provided the best results, followed by β-cyclodextrin. Increases in fluorescence emission by a factor of up to about 10 (mexiletine—fluorescamine—Triton X-100) were observed, with a generally negligible influence of the enhancing reagents on the excitation and emission maxima. Fluorescence enhancement by the addition of a suitable reagent solution to the final analyte solution may, in specific instances, enhance the detectability of native or chemically induced fluorophores.     

Thermal decomposition of HO2NO2 (peroxynitric acid, PNA): rate coefficient and determination of the enthalpy of formation

Rate coefficients for the gas-phase thermal decomposition of HO(2)NO(2) (peroxynitric acid, PNA) are reported at temperatures between 331 and 350 K at total pressures of 25 and 50 Torr of N(2). Rate coefficients were determined by measuring the steady-state OH concentration in a mixture of known concentrations of HO(2)NO(2) and NO. The measured thermal decomposition rate coefficients k(-)(1)(T,P) are used in combination with previously published rate coefficient data for the HO(2)NO(2) formation reaction to yield a standard enthalpy for reaction 1 of Delta(r)H degrees (298K) = -24.0 +/- 0.5 kcal mol(-1) (uncertainties are 2sigma values and include estimated systematic errors). A HO(2)NO(2) standard heat of formation, Delta(f)H degrees (298K)(HO(2)NO(2)), of -12.6 +/- 1.0 kcal mol(-1) was calculated from this value. Some of the previously reported data on the thermal decomposition of HO(2)NO(2) have been reanalyzed and shown to be in good agreement with our reported value.     

Nucleophile‐Dependent Regio‐ and Stereoselective Ring Opening of 1‐Azoniabicyclo[3.1.0]hexane Tosylate

1‐[(1R)‐(1‐Phenylethyl)]‐1‐azoniabicyclo[3.1.0]hexane tosylate was generated as a stable bicyclic aziridinium salt from the corresponding 2‐(3‐hydroxypropyl)aziridine upon reaction with p‐toluenesulfonyl anhydride. This bicyclic aziridinium ion was then treated with various nucleophiles including halides, azide, acetate, and cyanide in CH₃CN to afford either piperidines or pyrrolidines through regio‐ and stereoselective ring opening, mediated by the characteristics of the applied nucleophile. On the basis of DFT calculations, ring‐opening reactions under thermodynamic control yield piperidines, whereas reactions under kinetic control can yield both piperidines and pyrrolidines depending on the activation energies for both pathways.     

In situ EPR spectroscopy of aromatic diyne cyclopolymerization

Electron paramagnetic resonance (EPR) spectroscopy was successfully used for the first time to follow the Bergman cyclization of bis-ortho-diynyl arene (BODA) compounds. Five BODA monomers with different spacer (X) and terminal groups (R) were compared. In situ polymerization via EPR spectroscopy yielded first-order rate expressions. Monomers with spacer -O- or -C(CF(3))(2) and terminal group R = Ph exhibited similar kinetic behavior upon thermal polymerization, whereas monomers with pyridine and thiophene terminal groups gave significantly higher rates of polymerization over phenyl-terminated derivatives. A model compound, 1,2-bis(phenylethynyl)benzene, was used to probe the polymerization mechanism, and radical intermediates were found to be stable indefinitely at room temperature.     

Identification of Intermediates in Zeolite‐Catalyzed Reactions by In Situ UV/Vis Microspectroscopy and a Complementary Set of Molecular Simulations

The optical absorption properties of (poly)aromatic hydrocarbons occluded in a nanoporous environment were investigated by theoretical and experimental methods. The carbonaceous species are an essential part of a working catalyst for the methanol‐to‐olefins (MTO) process. In situ UV/Vis microscopy measurements on methanol conversion over the acidic solid catalysts H‐SAPO‐34 and H‐SSZ‐13 revealed the growth of various broad absorption bands around 400, 480, and 580 nm. The cationic nature of the involved species was determined by interaction of ammonia with the methanol‐treated samples. To determine which organic species contribute to the various bands, a systematic series of aromatics was analyzed by means of time‐dependent density functional theory (TDDFT) calculations. Static gas‐phase simulations revealed the influence of structurally different hydrocarbons on the absorption spectra, whereas the influence of the zeolitic framework was examined by using supramolecular models within a quantum mechanics/molecular mechanics framework. To fully understand the origin of the main absorption peaks, a molecular dynamics (MD) study on the organic species trapped in the inorganic host was essential. During such simulation the flexibility is fully taken into account and the effect on the UV/Vis spectra is determined by performing TDDFT calculations on various snapshots of the MD run. This procedure allows an energy absorption scale to be provided and the various absorption bands determined from in situ UV/Vis spectra to be assigned to structurally different species.