Evaluation of the enthalpy of formation, proton affinity, and gas-phase basicity of gamma-butyrolactone and 2-pyrrolidinone by isodesmic reactions

The knowledge of thermochemical parameters such as the enthalpy of formation, gas-phase basicity, and proton affinity may be the key to understanding molecular reactivity. The obtention of these thermochemical parameters by theoretical chemical models may be advantageous when experimental measurements are difficult to accomplish. The development of ab initio composite models represents a major advance in the obtention of these thermochemical parameters,. but these methods do not always lead to accurate values. Aiming at achieving a comparison between the ab initio models and the hybrid models based on the density functional theory (DFT), we have studied gamma-butyrolactone and 2-pyrrolidinone with a goal of obtaining high-quality thermochemical parameters using the composite chemical models G2, G2MP2, MP2, G3, CBS-Q, CBS-4, and CBS-QB3; the DFT methods B3LYP, B3P86, PW91PW91, mPW1PW, and B98; and the basis sets 6-31G(d), 6-31+G(d), 6-31G(d,p), 6-31+G(d,p), 6-31++G(d,p), 6-311G(d), 6-311+G(d), 6-311G(d,p), 6-311+G(d,p), 6-311++G(d,p), aug-cc-pVDZ, and aug-cc-pVTZ. Values obtained for the enthalpies of formation, proton affinity, and gas-phase basicity of the two target molecules were compared to the experimental data reported in the literature. The best results were achieved with the use of DFT models, and the B3LYP method led to the most accurate data.

Estimation of standard enthalpy of formation of alkanes in gaseous state by calculating size, structural and electronic parameters in the molecules

A quantitative analysis is made on the correlation ship of thermodynamic property, i.e., standard enthalpy of formation (ΔH fº) with Kier's molecular connectivity index(¹Xv),vander waal's volume (Vw) electrotopological state index (E) and refractotopological state index (R) in gaseous state of alkanes. The regression analysis reveals a significant linear correlation of standard enthalpy of formation (ΔH fº) with ¹Xv, Vw, E and R. The equations obtained by regression analysis may be used to estimate standard enthalpy of formation (ΔH fº) of alkanes in gaseous state.

Synthesis, mechanism of formation, and molecular orbital calculations of arylamidoximes

A simple and easy synthesis of ten arylamidoximes from arylnitriles and hydroxylamine is described. The formation of the arylamides has been observed to a much lesser extent in the present work. A new mechanism for the formation of arylamidoximes, as well as arylamides, from arylnitriles and hydroxylamine is suggested. Quantum mechanical calculations have been carried out to support this mechanism. The enthalpy of formation in conjunction with atomic charges of the reactants and intermediates helped to understand more about the generation of the products.

The Gibbs free energy of formation of a glass alloy

A simple expression for the Gibbs free energy of formation of a pure component or a eutectic alloy glass, relative to the stable crystalline phase (or phases) at the same temperature is deduced by use of thermodynamic arguments. The expression obtained is supposed to apply to both monocomponent and multicomponent liquid alloys that might become glasses from the supercooled liquid state, irrespective of the critical cooling rate needed to avoid crystallization.

Heats of formation of some hydrates /|nA. Phillipson. -- 260 St. Catharines, Ont. : [s. n.],

A great deal of data on the heats of formation of various hydrates has been compiled i n the J.A.N.A.F. and other tables such as the National Bureau of Standards circulars. Comparison of the heat of f ormation of a hydrate with that of the corresponding anhydrate exposes anomalies i n a surprising number of cases. Some of the results are so discordant that i t is apparent that one or the other value is seriously mistaken. No attempt has been made i n this work to determine which value may be correct, but measurements have been made of the difference between these two values. The procedure adopted has been to dissolve the hydrate and the anhydrate, to achieve the same final concentration of the compound in solution, and so to measure the difference in heats of solution .. Measurements were made at OOC in a modified Bunsen ice calorimeter, well insulated and surrounded by an icewater mixture . The observed differences in heats of solut ion were corrected t o 25°0 by using appropriate heat capacity data. These differences offer a direct measure of the enthalpy involved in binding a mole of water into the crystal structure and so should shed light on the nature of binding involved. The following hydrates were studied : MgS04.nH20 (n = 1,4,7), MnC12.nH20 (n = 1, 2), LiI. nH20 (n = 1,3), MnS04. nH20 (n = 1,4), CaC12. nH20 (n = 2,6) , K2C03.1~H20, LiCl.H20, LiBr.2H20, CdC12.2t H2o, and N2H4eH20.

Mechanisms of formation and function of eosinophil lipid bodies: inducible intracellular sites involved in arachidonic acid metabolism

Lipid bodies, inducible lipid-rich cytoplasmic inclusions, are characteristically abundant in cells associated with inflammation, including eosinophils. Here we reviewed the formation and function of lipid bodies in human eosinophils. We now have evidence that the formation of lipid bodies is not attributable to adverse mechanisms, but is centrally mediated by specific signal transduction pathways. Arachidonic acid and other cis fatty acids by an NSAID-inhibitable process, diglycerides, and PAF by a 5-lipoxygenase dependent pathway are potent stimulators of lipid body induction. Lipid body formation develops rapidly by processes that involve PKC, PLC, and de novo mRNA and protein synthesis. These structures clearly serve as repositoires of arachidonyl-phospholipids and are more than inert depots. Specific enzymes, including cytosolic phospholipase A2, MAP kinases, lipoxygenases and cyclooxygenases, associate with lipid bodies. Lipid bodies appear to be dynamic, organelle-like structures involved in intracellular pathways of lipid mobilization and metabolism. Indeed, increases in lipid body numbers correlated with enhanced production of both lipoxygenase- and cyclooxygenase-derived eicosanoids. We hypothesize that lipid bodies are distinct inducible sites for generating eicosanoids as paracrine mediators with varied activities in inflammation. The capacity of lipid body formation to be specifically and rapidly induced in leukocytes enhances eicosanoid mediator formation, and conversely pharmacologic inhibition of lipid body induction represents a potential novel and specific target for anti-inflammatory therapy.

The mechanism of formation of the mixed boron trihalide adducts of trimenthylamine

Boron trihalide and mixed boron trihalide adducts of trimethylamine have been prepared, and characterized by proton and fluorine N.M.R. spectroscopy. The acceptor power of the boron trihalides was seen to increase in the order BF3 < BC13 < BBr3 < BI3, corroborating previous evidence. The mixed boron trihalides had intermediate Lewis acidities. Solution reactions between adducts and free boron trihalides rapidly led to the formation of mixed adducts when the free boron trihalide is a stronger Lewis acid than that in the adduct. A slower reaction is observed when the free BX3 is a weaker Lewis aoid than that complexed. The mechanism of halogen exchange leading to the mixed (CH3)3NBX3 adducts was investigated. 10B labelling experiments precluded B-N bond rupture as a possible mechanism in solution; results are discussed in terms of halogen-bridged intermediates. Pre-ionization may be important for some systems. At higher temperatures, during gas phase reactions,B-N coordinate bond rupture may be the initial step of reaction. Two mixed adduots, namely (CH3)3NBClBr2 and (CH3)3NBHOIBr were prepared and characterized by Mass Spectrometry

Structural And Surface Morphological Investigation Of Formation Stages Of Highly (002) Oriented Zno Films On Glass Substrates By Spray Pyrolysis Method

ZnO thin films were coated on amorphous glass substrate at various temperatures in the range 160-500 0C by spray pyrolysis method. The as deposited films were characterised by using XRD and SEM. Wurtzite phase of ZnO was formed at a substrate temperature of 400 0C, highly oriented (002) phase was developed with respect to increase of substrate temperature from 450 to 500 0C. Morphological and growth mode of these films were analyzed with respect to structural orientation of films from wurtzite to highly (002) oriented phase. Present study reveals that substrate temperature was one of the important parameters which determine the crystalline quality, population of defects, grain size, orientation and morphology of the films

Cyclopropylidenes, bicyclopropylidenes, and vinylcarbenes - some modes of formation and preparative applications

The routes of transformation of the simplest bicyclopropylidene into the derivatives of the second and third generations and synthesis of perspirocyclopropanated [3]rotane and linear spiral [4]- and [5]triangulanes are discussed.

Synthesis, structure and solution chemistry of dioxidovanadium(V) complexes with a family of hydrazone ligands. Evidence of formation of centrosymmetric dimers via H-bonds in the solid state

[(VO)-O-IV(acac) 2] reacts with the methanol solution of tridentate ONO donor hydrazone ligands (H2L1-4, general abbreviation H2L; are derived from the condensation of benzoyl hydrazine with 2-hydroxyacetophenone and its 5-substituted derivatives) in presence of neutral monodentate alkyl amine bases having stronger basicity than pyridine e. g., ethylamine, diethylamine, triethylamine and piperidine (general abbreviation B) to produce BH+[VO2L] (1-16) complexes. Five of these sixteen complexes are structurally characterized revealing that the vanadium is present in the anionic part of the molecule, [VO2L] in a distorted square pyramidal environment. The complexes 5, 6, 15 and 16 containing two H-atoms associated with the amine-N atom in their cationic part (e. g., diethylammonium and piperidinium ion) are involved in H-bonding with a neighboring molecule resulting in the formation of centrosymmetric dimers while the complex 12 (containing only one hydrogen atom in the cationic part) exhibits normal H-bonding. The nature of the H-bonds in each of the four centrosymmetric dimeric complexes is different. These complexes have potential catalytic activity in the aerial oxidation of L-ascorbic acid and are converted into the [VO(L)(hq)] complexes containing VO3+ motif on reaction with equimolar amount of 8-hydroxyquinoline (Hhq) in methanol.

Exploring new molecular species on the (1)[H, Se, F] singlet potential energy surface: Energetics, structures, IR spectra, and heats of formation

Structural, energetic, and vibrational properties of new molecular species, HSeF and HFSe, the associated transition state, and dissociation fragments are investigated using a state-of-the-art theoretical approach, CCSD(T)/CBS. HSeF is a normal covalently bonded molecule 38.98 kcal mol (1) more stable than the complex HF-Se, which shows an unusual structure with a central fluorine atom and a bond angle of 101.8 degrees.A barrier (Delta G(#)) of 49.01 kcal mol (1) separates the two species. Vibrational frequencies are also quite distinct. Heats of formation are evaluated for the diatomic fragments and HSeF. Final Delta(f)H values depend on the experimental accuracy of those of Se(g) and H(2)Se. (c) 2009 Elsevier B.V. All rights reserved.

Action of auxins and/or boron, in the process of formation of roots in cuttings of coffee (Coffea-Arabica L CV Mundo-Novo)

The objective of present research was to verify the IBA and/or NAA effects with boron, on rooting of coffee (Coffea arabica L. cv 'Mundo Novo') stem cuttings. Therefore it were used stem cuttings from semi-hardwood orthotropous branches, having two nodes, with aproximately 10 cm of lenght. The cuttings were treateds during 24 hours with IBA and/or NAA plus boron solutions. The treatments' effect was observed trough the following observation, 90 days after planting: rooting percentage and number of cuttings with ''callus''. Trough the resultS obtained, it was concluded that, for obtaining more rooting of cuttings, the best treatment was NAA at 200 ppm plus boron or, the combination of IBA and NAA at 200 ppm plus boron.

SAXS study of the kinetics of formation of ZnO colloidal suspensions

We have investigated, by in situ small-angle X-ray scattering (SAXS), the kinetics of formation of zinc oxide colloidal suspensions obtained after refluxing alcoholic solution of zinc acetate and catalysed by lithium hydroxide. The experimental results demonstrate that the suspensions are composed of colloidal spheroidal particles with a multimodal size distribution. The average radius of the main mode, approximately 2 nm, is invariant but the number of these basic particles continuously increases for increasing hydrolysis reaction time. The other two modes correspond to particles with average radii close to 6 and 10 nm, respectively. The larger particles are formed by coagulation of the smaller ones. (C) 1999 Elsevier B.V. B.V. All rights reserved.

SAXS study of formation and growth of tin oxide nanoparticles in the presence of complexing ligands

The effect of acetylacetone (acac) complexing ligand on the formation and growth of tin oxide-based nanoparticles during thermohydrolysis at 70 degreesC of a tin precursor SnCl4-n(acac)(n) (0 less than or equal to n less than or equal to 2) solution was analyzed by in situ small-angle X-ray scattering. A. transparent and stable sol was obtained after 2 h of thermohydrolysis at 70 degreesC, allowing the quantitative determination of the particle volume distribution function and its variation with the reaction time. The number of colloidal particles for equivalent thermohydrolysis temperature and time decreases as the [acac]/[Sn] ratio in initial solution increases from 0.5 to 6. Instead, the amount of soluble species remaining in solution increases for increasing [acac]/[Sn] ratio within the same range. This indicates that increasing amounts of Sn-acetylacetone complexes partially prevent the hydrolysis and consequent formation of colloidal particles. The N-2 adsorption isotherm characterization of freeze-dried powders demonstrates that the average pore size is approximately equal to the average size (approximate to9 Angstrom) of the colloidal primary particles in the sol, and that the porosity and surface area (approximate to200 m(2) g(-1)) are independent of the acac content in the initial solution.