Search results for "DEUTERIUM"
showing 10 items of 470 documents
Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation
2017
Abstract Synthesis, characterization and reaction chemistry of lutetium alkylamido LLu(CH2SiMe3)(NHCPh3) (2), L = 2,5-[Ph2P=N(4-iPrC6H4)]2N(C4H2)–, is reported. Complex 2 undergoes cyclometalation of the NHCPh3 ligand at elevated temperatures to produce the orthometalated complex LLu(κ2−N,C-(NHCPh2(C6H4))) (3) which converts to 0.5 equivalents of bis(amido) LLu(NHCPh3)2 (4) upon heating at 80 °C for 24 h. Reaction of complex 2 with 4-dimethylaminopyridine (DMAP) does not promote alkane elimination nor imido formation. A kinetic analysis of the thermal decomposition of complex 2, supported by deuterium labelling studies and computational analysis (PBE0/def2-TZVP/SDD(Lu)), indicate direct Csp…
H-2, H-3(+) and the age of molecular clouds and prestellar cores
2012
Measuring the age of molecular clouds and prestellar cores is a difficult task that has not yet been successfully accomplished although the information is of paramount importance to help in understanding and discriminating between different formation scenarios. Most chemical clocks suffer from unknown initial conditions and are therefore difficult to use. We propose a new approach based on a subset of deuterium chemistry that takes place in the gas phase and for which initial conditions are relatively well known. It relies primarily on the conversion of H 3 + into H 2D + to initiate deuterium enrichment of the molecular gas. This conversion is controlled by the ortho/para ratio of H2 that i…
Lagrangian simulations of stable isotopes in water vapor: An evaluation of nonequilibrium fractionation in the Craig-Gordon model
2009
[1] The Craig-Gordon model is the basis for the parameterization of water isotope fractionation during evaporation from the ocean in many atmospheric isotope models. Its exact formulation (e.g., with respect to the nonequilibrium fractionation factor k) is mainly based on theoretical considerations and not very well constrained by observations. This study addresses this issue by combining a recently developed Lagrangian moisture source analysis with a Craig-Gordon fractionation parameterization for the identified evaporation events in order to model isotope ratios in water vapor. This technique is applied to 45 measurement days of isotopes in water vapor at Rehovot (Israel) during the years…
Isotopic Effect on the Kinetics of the Belousov-Zhabotinsky Reaction
2007
In this work we present results about the deuterium isotope effect on the global kinetics of a Belousov-Zhabotinsky reaction in batch conditions. A nonlinear dependence of the Induction Period upon the percentage of deuterated reactants was found. The isotopic effect on the bromination reaction of malonic acid was evaluated.
Observations of molecular hydrogen (H2) mixing ratio and stable isotopic composition (deuterium content) at the Cabauw tall tower in the Netherlands
2016
This zip file contains the final corrected data that were used for the journal article "Observations of molecular hydrogen mixing ratio and stable isotopic composition at the Cabauw tall tower in the Netherlands" by Batenburg et al., Atmospheric Environment, 2016, doi:10.1016/j.atmosenv.2016.09.058 Please cite the original AtmosEnv article when using these data. The paper also contains more information about how these data were collected and calibrated, and on how the quality control flags were assigned. All samples were collected at the Cabauw tower, at the CESAR site (51.971° N, 4.927° E, http://www.cesar-observatory.nl/). H2 and deltaD(H2) are calibrated using one to four laboratory re…
Studies in organic mass spectrometry. Part 24† Electron ionization mass spectra of some aryl(2-nitrobenzo[b]thiophen-3-yl)amines
1999
The main fragmentation routes of eighteen title compounds and of three 5-chloro derivatives have been investigated with the aid of linked scan (B/E = constant) spectrometry, accurate mass measurements and deuterium labelling. Copyright © 1999 John Wiley & Sons, Ltd.
Magnetic Excitations in Polyoxometalate Clusters Observed by Inelastic Neutron Scattering: Evidence for Ferromagnetic Exchange Interactions and Spin…
1999
The ground-state properties of the tetranuclear Ni2+ cluster [Ni4(H2O)2(PW9O34)2]10- were investigated by combining magnetic susceptibility and magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated sample of K6Na4[Ni4(H2O)2(PW9O34)2]·24H2O. The temperature dependence of the magnetic susceptibility indicates a ferromagnetic coupling of the four constituent Ni2+ ions (s = 1), and a low-temperature magnetization study provides the magnitude of the S = 4 ground-multiplet splitting due to the single-ion anisotropy of the Ni2+ ions. Besides a more direct and precise determination of the anisotropic S = 4 ground-multiplet splitting, INS enabled t…
Deuterium isotope effect on the induction period of the cerium catalyzed Belousov-Zhabotinsky reaction
2009
Abstract In this work we present results about the deuterium isotopic effect on the global kinetics of a cerium catalyzed Belousov–Zhabotinsky reaction. A nonlinear dependence of the induction period upon the percentage of deuterated reactants was found in batch conditions. In order to understand this result, we investigated two reaction pathways responsible for the length of the induction period, namely: (a) the reaction between the enolic form of the malonic acid with molecular bromine and (b) the oxidation of malonic acid by the Ce(IV) ion. In both cases we obtained a linear dependence of the kinetic constants on the percentage of deuterated reactants. Nevertheless, by inserting the expe…
Mass spectra of chlorinated aromatics formed in pulp bleaching: I—chlorinated catechols
1983
The fragmentation of chlorinated guaiacols (2-methoxyphenols) on electron impact has been studied. The most common fragmentation processes are interpreted and in some cases the small differences between spectra of positional isomers are explained. In addition to the well-known alkyl-oxygen fission (loss of methyl radical), metastable ion studies and deuterium labelling have indicated several new fragmentation pathways. The most characteristic are the formation of [MCH3HCl]+ and [MCH3Cl]+· ions. In general, however, the spectra of positional isomers are shown to be very similar.
Electron impact mass spectra of chlorinated methyl propanoates
1982
The mass spectral fragmentations of all eleven chlorinated methyl propanoates have been studied. Deuterium labelling and metastable ion analysis were used to elucidate the fragmentation mechanism. The molecular ion peaks of all compounds are small, except methyl 3,3-dichloropanoate (38%). In most cases α-cleavage gives the base peak [COOCH3]+, and the loss of a chlorine atom from the molecular ion is characteristic of the 3-chloro, 3,3-dichloro and 3,3,3-trichloro compounds. Metastable ions showed the losses of small neutral molecules such as CH3OH, CH2CO, CO2 and CO from the [MCl]+ ion. α-Cleavage and the loss of Cl˙ gives an intense [MCOOCH3Cl]+˙ peak, which is the base peak in the spectr…