Reactions of hydroxyl radicals with trichloroethene and tetrachloroethene in argon matrices at 12 K

Irradiation of argon matrices at 12 K containing hydrogen peroxide and tetrachloroethene using the output from a medium-pressure mercury lamp gives rise to the carbonyl compound trichloroacetyl chloride (CCl3CClO). Similarly trichloroethene gives dichloroacetyl chloride ( CCl2HCClO) - predominantly in the gauche form - under the same conditions. It appears that the reaction is initiated by homolysis of the O-O bond of H2O2 to give OH radicals, one of which adds to the double bond of an alkene molecule. The reaction then proceeds by abstraction of the H atom of the hydroxyl group and Cl-atom migration. This mechanism has been explored by the use of DFT calculations to back up the experimental findings. The mechanism is analogous to that shown by the simple hydrocarbon alkenes.

Syntheses and crystal structures of [Sn{2-[(Me3Si)2C]C5H4N}R] [R = C6H2Pri3-2,4,6 1 or CH(PPh2)2 2], two novel heteroleptic tin(II) compounds derived from [Sn-{2-[(Me3Si)2C]C5H4N}Cl], and for [{Sn(C6H2Pri3-2,4,6)2}3] 3, a structural redetermination

Two novel, monomeric heteroleptic tin(II) derivatives, [Sn{2-[(Me3Si)2C]C5H4N}R] [R = C6H2Pri3-2,4,6 1 or CH(PPh2)2 2], have been prepared, characterised by multinuclear NMR spectroscopies and their molecular structures determined by single crystal X-ray diffraction. Both compounds were prepared from the corresponding heteroleptic tin(II) chloro-analogue, [Sn{2-[(Me3Si)2C]C5H4N}Cl], and thus demonstrate the utility of this compound as a precursor to further examples of heteroleptic tin(II) derivatives: such compounds are often unstable with respect to ligand redistribution. In each case, the central tin(II) is three-co-ordinate. Crystals of trimeric [{Sn(C6H2Pri3-2,4,6)2}3] 3 were found to undergo a solid state phase transition, which may be ascribed to ordering of the ligand isopropyl groups. At 220 K the unit cell is orthorhombic, space group Pna21, compared with monoclinic, space group P21/c, for the same crystals at 298 K, in which there is an effective tripling of the now b (originally c) axis. This result illustrates the extreme crowding generated by this bulky aryl ligand.

Preparation, characterization, and CuX2 and CoX2 (X = Cl-, Br-, ClO4-) adsorption behavior of a polyhedral oligomer silsesquioxane functionalized with an organic base

In this paper we report on the synthesis, characterization, and adsorption properties of the first 3-amino-1,2,4-triazole-modified porous silsesquioxane (ATPS). The isotherms of adsorption of MX2 (M = Cu(II), Co(II); X = Cl-, Br-, ClO4-) by ATPS were studied in ethanol and aqueous solutions at 298 K. The results showed that there is a good fit between the experimental data and the Langmuir isotherm. The adsorption capacity in both solvents followed the sequence Cu(II) >> Co(II). The lowest adsorption for Co(II) should be related to the largest hydration volume, which obstructs the adsorption capacity of the surface, and consequently causes a decrease in the number of cations adsorbed. For the salts with different anions the sequence was MCl2 > MBr2 > M(ClO4)2 in both solvents. The low affinity for M(ClO4)(2) toward the solid phase is a consequence of the poorer coordination ability of the ClO4-. Adsorptions from ethanol solutions were higher than those from aqueous solutions due to the higher polarity of water, which can more strongly solvate the solute and the basic sites on the surface. The following adsorption capacities (in mmol g(-1)) were determined: 0.24 (aq) and 0.84 (eth) for CuCl2, 0.09 (aq) and 0.16 (eth) for CuBr2, and 0.08 (aq) and 0.11 (eth) for Cu(ClO4)(2); 0.02 (aq) and 0.07 (eth) for CoCl2, 0.02 (aq) and 0.06 (eth) for CoBr2, and 0.01 (aq) and 0.05 (eth) for Co(ClO4)(2). (c) 2007 Elsevier B.V. All rights reserved.

Synthesis and reactivity in salt metathesis reactions of trivalent [La(Tp(Me2))(2)X] (X = Cl, I) complexes: crystal structures of [La(Tp(Me2))(2)Cl] and [La(Tp(Me2))(2)(kappa(2)-pz(Me2))]

Reaction of LaX3(THF)(n) (X = Cl, 1) with two equiv. of K(Tp(Me2)) gave good yields of the bis-Tp complexes [La(Tp(Me2))(2)X] (X = Cl (1); I (3)). However, the formation of 1 and 3 is always accompanied by significant amounts of La(Tp(Me2))(2)(kappa(2)-pz(Me2)) ([pz(Me2)](-) = 3,5-dimethyl-pyrazolato) (2). The pyrazolato complex 2, which presumably arises from decomposition of the [Tp(Me2)](-) moiety during salt metathesis, was independently prepared in good yield from 1 and in situ generated [pz(Me2)](-). The solid-state structures of 1 and 2 were determined by single-crystal X-ray diffraction studies. Subsequent reactions of halogeno-Tp(Me2) complexes 1 and 3 with various alkali metal salts MR (M = Li, R = CH2SiMe3, Ph, N(SiMe3)(2); M = K, R = OAr) gave M(Tp(Me2)) as the major product. Alternatively, the mono-Tp bis(aryloxide) derivatives [Ln(Tp(Me2))(OC6H2-2,6-'Bu-4-Me)(2)] (Ln = La (4); Nd (5)) were obtained in high yields by salt metathesis of [Ln(OC6H2-2,6-'Bu-4-Me)(3)] with one equiv. of K(Tp(Me2)). (C) 2004 Elsevier Ltd. All rights reserved.

Mono- and dinuclear palladium(II) compounds containing nitrogen ligands. Crystal and molecular structure of [Pd(N,C-dmba)(NCO)(2,3-lut)] and [Pd(H2CCOMe)Cl(2,2 '-bipy)]

The cyanate-bridged cyclopalladated compound [Pd(N,C-dmba)(mu-NCO)](2) (1) (dmba = PhCH2NMe2) reacts in CH2Cl2 with 2,3-lutidine (2,3- lut), 3,4-lutidine (3,4-lut), 2,2'-bipyridine (2,2'-bipy) and 4,4'-bipyridine (4,4'-bipy), to give [Pd(N, C-dmba)(NCO)(2,3-lut)] (2), [Pd(N,C-dmba)(NCO)(3,4-lut)] (3), [{Pd(N,C-dmba)(NCO)}(2)(mu-2,2'-bipy)] .CH2Cl2 (4) and [{Pd(N,C-dmba)(NCO)}(2)(mu-4,4'-bipy)] . CH2Cl2 (5), respectively. The compounds were characterized by elemental analysis, i.r. and n. m. r. spectroscopy and also by t.g.a. The i.r. spectra of (2 - 5) display typical bands of monodentate N-bonded cyanate groups, whereas the n. m. r. data of (4) are consistent with the presence of a bridging 2,2'-bipyridine ligand. Complex (4) decomposes slowly in acetone. One of the products formed, [Pd(H2CCOMe) Cl(2,2'-bipy)] (6), was characterized by X-ray diffraction. As inferred from the t.g.a., the thermal stability decreases in the order: [{Pd(N,C-dmba)(NCO)}(2) (mu-4,4'-bipy)]. CH2Cl2 (5) > [Pd(N,C-dmba)(2,3-lut)( NCO)] (2) = [Pd(N, C-dmba)(3,4-lut)(NCO)] (3) > [{Pd(N,C-dmba)(NCO)}(2)(mu- 2,2'-bipy)] .CH2Cl2 (4). According to thermal analysis and X-ray diffraction patterns compounds (2 - 3) decompose into metallic palladium Pd(0), whereas (4 - 5) decompose with the formation of PdO. The X-ray crystal and molecular structure of [Pd(N, C-dmba)( NCO)(2,3-lut)] (2) was determined. The lutidine unit is perpendicular to the coordination plane.

Crystal structure of potassium trifluoro[1,3-dithiano]borate, K(C4S2H7BF3)

C4H7BF3KS2, monoclinic, P12(1)/cl (no. 14), a = 14.7374(3) angstrom, b = 9.06121) angstrom, c = 13.5805(2) angstrom, beta = 98.964(4)degrees, V = 1791.4 angstrom(3), Z = 8, R-gt(F) = 0.029, wR(ref)(F-2) = 0.010, T = 296 K.

Migração de K+, Cu2+ e CI- em solos do subgrupo Itararé no Estado de São Paulo: ensaios sorcivos, percolação em colunas e simulações geoquímicas

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Binary liquid-liquid equilibria for systems of mono or disubstituted haloakanes (Cl,Br) and pyiridinium based ionic liquids. Advances in the experimentation and interpretation of results

[EN]This work presents the measurements made to define the temperature−composition curves for a set of binary systems composed of several pyridinium-based ionic liquids (ILs) [bpy][BF4] and [bYmpy][BF4] (Y = 2,3,4) with mono- and dihaloalkanes (Cl and Br) in the temperature interval [280−473] K and at atmospheric pressure. With the exception of the short chain dichloroalkanes (1,1- and 1,2-), all the compounds present some degree of immiscibility with the ionic liquids selected.

Messung der K 0 L e + e - e + e - und K 0 L my + my - e + e - Zerfallsraten

Das NA48 Experiment am CERN misst die direkte CP-Verletzung im System der neutralen Kaonen aus der Zerfallsrate von kurzlebigen undlanglebigen neutralen Kaonen in zwei Pionen.Des Weiteren gestattet der experimentelle Aufbau den Nachweis seltenener Kaonzerfaelle.In dieser Dissertation werden Zerfaelle des langlebigen Kaons in Endzustaende mit vier Leptonen untersucht. Fuer das Verzweigungsverhaeltnis von K_L -> e+e-e+e- ergibt sich(3.94E-8 +/- 0.40E-8).Fuer das von K_L -> mu+mu-mu+mu- ergibt sich (3.08E-9 +/- 0.71E-9).Fuer den Leptonenzahl verletzenden ZerfallK_L -> mu(+/-)mu(+/-)e(-/+)e(-/+) wirdeine obere Grenze von 3.5E-10 (CL=90%) gesetzt.

Pseudodifferential analysis in Psi*-algebras on transmission spaces, infinite solving ideal chains and K-theory for conformally compact spaces

The present thesis is a contribution to the theory of algebras of pseudodifferential operators on singular settings. In particular, we focus on the $b$-calculus and the calculus on conformally compact spaces in the sense of Mazzeo and Melrose in connection with the notion of spectral invariant transmission operator algebras. We summarize results given by Gramsch et. al. on the construction of $Psi_0$-and $Psi*$-algebras and the corresponding scales of generalized Sobolev spaces using commutators of certain closed operators and derivations. In the case of a manifold with corners $Z$ we construct a $Psi*$-completion $A_b(Z,{}^bOmega^{1/2})$ of the algebra of zero order $b$-pseudodifferential operators $Psi_{b,cl}(Z, {}^bOmega^{1/2})$ in the corresponding $C*$-closure $B(Z,{}^bOmega^{12})hookrightarrow L(L^2(Z,{}^bOmega^{1/2}))$. The construction will also provide that localised to the (smooth) interior of Z the operators in the $A_b(Z, {}^bOmega^{1/2})$ can be represented as ordinary pseudodifferential operators. In connection with the notion of solvable $C*$-algebras - introduced by Dynin - we calculate the length of the $C*$-closure of $Psi_{b,cl}^0(F,{}^bOmega^{1/2},R^{E(F)})$ in $B(F,{}^bOmega^{1/2}),R^{E(F)})$ by localizing $B(Z, {}^bOmega^{1/2})$ along the boundary face $F$ using the (extended) indical familiy $I^B_{FZ}$. Moreover, we discuss how one can localise a certain solving ideal chain of $B(Z, {}^bOmega^{1/2})$ in neighbourhoods $U_p$ of arbitrary points $pin Z$. This localisation process will recover the singular structure of $U_p$; further, the induced length function $l_p$ is shown to be upper semi-continuous. We give construction methods for $Psi*$- and $C*$-algebras admitting only infinite long solving ideal chains. These algebras will first be realized as unconnected direct sums of (solvable) $C*$-algebras and then refined such that the resulting algebras have arcwise connected spaces of one dimensional representations. In addition, we recall the notion of transmission algebras on manifolds with corners $(Z_i)_{iin N}$ following an idea of Ali Mehmeti, Gramsch et. al. Thereby, we connect the underlying $C^infty$-function spaces using point evaluations in the smooth parts of the $Z_i$ and use generalized Laplacians to generate an appropriate scale of Sobolev spaces. Moreover, it is possible to associate generalized (solving) ideal chains to these algebras, such that to every $ninN$ there exists an ideal chain of length $n$ within the algebra. Finally, we discuss the $K$-theory for algebras of pseudodifferential operators on conformally compact manifolds $X$ and give an index theorem for these operators. In addition, we prove that the Dirac-operator associated to the metric of a conformally compact manifold $X$ is not a Fredholm operator.

K-feldspar hygrochronology

The significance of the multi-isotopic record preserved in K-feldspars is assessed on samples from the Aar metagranite, Central Alps, Switzerland having very tight independent geological constraints. Stepwise leaching reveals that two diachronically grown K-feldspar generations coexist: Kfs-1 (≥ 35 Ma old, Ca-poor, Rb-Cl-rich, with low 87Sr/86Sr and high 206Pb/204Pb) and Kfs-2 (≤ 10 Ma old, antithetic isotopic signatures deriving from external fluids). Microtextures imaged by cathodoluminescence, backscattered electrons, and electron probe microanalysis are patchy and chemically heterogeneous, with pronounced enrichments in Ba in the retrogressed regions. This confirms the simultaneous presence of fluid-dominated retrogression and recrystallization and isotopic inheritance. The staircase-shaped 40Ar/39Ar age spectrum correlates with the Ca/K and Cl/K signatures. This reflects a mixture of heterochemical K-feldspar generations, and not an intracrystalline Ar gradient caused by diffusion. The shape of the age spectrum and the in vacuo release kinetics proceed from entirely different physical and geological phenomena. What K-feldspars can be effectively used for is to constrain the timing of the fluids that interacted with them by multi-isotopic analyses, rather than to model a “cooling history” from 39Ar release alone. The identification of multiple mineral generations by imaging combined with multi-isotopic analysis enables the accurate dating of the events of a multistage evolution after the initial crystallization of the rock in which the minerals occur.

Resolving Cl and SO4 Profiles in a Clay-Rich Rock Sequence

The chloride and sulfate concentration profiles in a 260 m thick clay-rich Mesozoic sediment sequence have been analyzed by various methods. Chloride data generally indicate a good consistency between different methods if anion exclusion is accounted for in leaching tests. For sulfate, however, there is an apparent inconsistency between leaching data and those obtained from the other methods, which points to the dissolution of a sulfur-bearing mineral. Traces of diagenetic gypsum seem to be a likely source, but other sulfur minerals cannot be ruled out.

Calibration of cosmogenic noble gas production in ordinary chondrites based on 36 Cl- 36 Ar ages. Part 1: Refined produced rates for cosmogenic 21 Ne and 38 Ar

We measured the concentrations and isotopic compositions of He, Ne, and Ar in bulk samples and metal separates of 14 ordinary chondrite falls with long exposure ages and high metamorphic grades. In addition, we measured concentrations of the cosmogenic radionuclides 10Be, 26Al, and 36Cl in metal separates and in the nonmagnetic fractions of the selected meteorites. Using cosmogenic 36Cl and 36Ar measured in the metal separates, we determined 36Cl-36Ar cosmic-ray exposure (CRE) ages, which are shielding-independent and therefore particularly reliable. Using the cosmogenic noble gases and radionuclides, we are able to decipher the CRE history for the studied objects. Based on the correlation 3He/21Ne versus 22Ne/21Ne, we demonstrate that, among the meteorites studied, only one suffered significant diffusive losses (about 35%). The data confirm that the linear correlation 3He/21Ne versus 22Ne/21Ne breaks down at high shielding. Using 36Cl-36Ar exposure ages and measured noble gas concentrations, we determine 21Ne and 38Ar production rates as a function of 22Ne/21Ne. The new data agree with recent model calculations for the relationship between 21Ne and 38Ar production rates and the 22Ne/21Ne ratio, which does not always provide unique shielding information. Based on the model calculations, we determine a new correlation line for 21Ne and 38Ar production rates as a function of the shielding indicator 22Ne/21Ne for H, L, and LL chondrites with preatmospheric radii less than about 65 cm. We also calculated the 10Be/21Ne and 26Al/21Ne production rate ratios for the investigated samples, which show good agreement with recent model calculations.

Calibration of cosmogenic noble gas production based on ³⁶Cl-³⁶Ar ages. Part 2. The ⁸¹Kr-Kr dating technique

We calibrated the ⁸¹Kr-Kr dating system for ordinary chondrites of different sizes using independent shielding-corrected ³⁶Cl-³⁶Ar ages. Krypton concentrations and isotopic compositions were measured in bulk samples from 14 ordinary chondrites of high petrologic type and the cosmogenic Kr component was obtained by subtracting trapped Kr from phase Q. The thus-determined average cosmogenic ⁷⁸Kr/⁸³Kr, ⁸⁰Kr/⁸³Kr, ⁸²Kr/⁸³Kr, and ⁸4Kr/⁸³Kr ratiC(Lavielle and Marti 1988; Wieler 2002). The cosmogenic ⁷⁸Kr/⁸³Kr ratio is correlated with the cosmogenic 22Ne/21Ne ratio, confirming that ⁷⁸Kr/⁸³Kr is a reliable shielding indicator. Previously, ⁸¹Kr-Kr ages have been determined by assuming the cosmogenic production rate of ⁸¹Kr, P(⁸¹Kr)c, to be 0.95 times the average of the cosmogenic production rates of ⁸⁰Kr and ⁸²Kr; the factor Y = 0.95 therefore accounts for the unequal production of the various Kr isotopes (Marti 1967a). However, Y should be regarded as an empirical adjustment. For samples whose ⁸⁰Kr and ⁸²Kr concentrations may be affected by neutron-capture reactions, the shielding-dependent cosmogenic (⁷⁸Kr/⁸³Kr)c ratio has been used instead to calculate P(⁸¹Kr)/P(⁸³Kr), as for some lunar samples, this ratio has been shown to linearly increase with (⁷⁸Kr/⁸³Kr)c (Marti and Lugmair 1971). However, the ⁸¹Kr-Kr ages of our samples calculated with these methods are on average ~30% higher than their ³⁶Cl-³⁶Ar ages, indicating that most if not all the ⁸¹Kr-Kr ages determined so far are significantly too high. We therefore re-evaluated both methods to determine P(⁸¹Kr)c/P(⁸³Kr)c. Our new Y value of 0.70 ± 0.04 is more than 25% lower than the value of 0.95 used so far. Furthermore, together with literature data, our data indicate that for chondrites, P(⁸¹Kr)c/P(⁸³Kr)c is rather constant at 0.43 ± 0.02, at least for the shielding range covered by our samples ([⁷⁸Kr/⁸³Kr]c = 0.119–0.185; [22Ne/21Ne]c = 1.083–1.144), in contrast to the observations on lunar samples. As expected considering the method used, ⁸¹Kr-Kr ages calculated either directly with this new P(⁸¹Kr)c/P(⁸³Kr)c value or with our new Y value both agree with the corresponding ³⁶Cl-³⁶Ar ages. However, the average deviation of 2% indicates the accuracy of both new ⁸¹Kr-Kr dating methods and the precision of the new dating systems of ~10% is demonstrated by the low scatter in the data. Consequently, this study indicates that the ⁸¹Kr-Kr ages published so far are up to 30% too high.