Xn:Harmful;
67-72-1Relevant articles and documents
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Lorette
, p. 843 (1957)
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Reaction of Tetrathiafulvalene with Haloalkanes
Vessal, Behnam,Miller, John G.
, p. 2695 - 2698 (1982)
A kinetic study of the photochemical rection of TTF with haloalkanes has been made.The results are largely in agreement with a mechanism suggested by Scott and co-workers, but some additional findings of fundamental importance were obtained.An improved photosynthesis of TTFCl0.68 is reported.
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Miller
, p. 993 (1940)
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Interaction of trichloromethane and tetrachloromethane with nitrogen trifluoride
Mukhortov,Pashkevich,Blinov,Kambur,Kambur,Petrov,Kurapova
, p. 420 - 426 (2011)
Interaction of nitrogen trifluoride with trichloromethane and tetrachloromethane at temperatures in the range from 20 to 200°C and pressures of up to 6.0 MPa in the gas and liquid phases was studied.
High-Pressure Studies of Radical-Solvent Molecule Interactions in the CCl3 and Bromine Combination Reactions of CCl3
Oum, Kawon,Luther, Klaus,Troe, Juergen
, p. 2690 - 2699 (2004)
The combination reactions CCl3 + CCl3 (+ M) → C2Cl6 (+ M) and CCl3 + Br (+ M) → CCl 3Br (+ M) (with rate constants of k1 and k2, respectively) were studied at temperatures of 250 and 300 K over the pressure range of 0.01-1000 bar. Helium, argon, xenon, N2, CO2, and SF6 were used as bath gases. CCl3 radicals were generated via the photolysis of CCl3Br at 248 nm, and their absorption was monitored at 223.5 nm. The limiting "high-pressure" rate constants within the energy-transfer mechanism were determined, independent of density and the choice of the bath gas, over the pressure range of 1-10 bar, to be k 1,∞(T) = (1.0 ± 0.2) × 10-11 (T/300 K)-0.17 cm3 molecule-1 s-1 and k2,∞(T) = (2.0 ± 0.2) × 10-11 (T/300 K)-0.13 cm3 molecule-1 s-1. In the helium, N, and argon bath gases, at pressures above ～40 bar, the reactions became increasingly faster when the pressure was further raised until they finally started to slow at densities where diffusion-controlled kinetics dominates. This is the first detailed report of such a peculiar density dependence of combination rate constants for larger radicals with five or eight atoms. Possible origins of these pressure effects, such as the influence of the radical-complex mechanism and the density dependence of electronic quenching, are discussed.
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Kailan
, p. 537,549 (1917)
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Carlsson et al.
, p. 4726 (1966)
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Kinetic Study of the Reactions CCl3 + O2 + M -> CCl3O2 + M from 1 to 760 Torr and from 233 to 333 K
Danis, F.,Caralp, F.,Rayez, T.,Lesclaux, R.
, p. 7300 - 7307 (1991)
The kinetics of reaction 1, CCl3 + O2 + M -> CCl3O2 + M, has been investigated in detail as a function of temperature and over a large pressure range.At low pressure, 0.8-12 Torr, the reaction was investigated by laser photolysis and time-resolved mass spectrometry, while at high pressure (760 Torr), flash photolysis with UV absorption spectrometry was employed.At the low pressure limit, the rate expression, k1(0) = (1.6 +/- 0.3) x 10-30(T/298)-(6.3+/-0.5) cm6 molecule-2 s-1 (M = N2), exhibits a quite strong negative temperature coefficient.The obtained strong collision rate expression, 7.0 x 10-30(T/298)-4.3 cm6 molecule-2 s-1, using either RRKM calculations or Troe's factorized expression, is unable to reproduce the experimental temperature dependence, unless an unreasonably strong temperature dependence is assigned to the collisional efficiency factor: βc = 0.23(T/298)-2.0 (M = N2).Similar results are obtained for other chlorofluoromethyl radicals.The falloff curves were constructed by using RRKM calculations obtained by adjusting βc and the transition-state model, in order to reproduce the experimental data.The rate expression at the high-pressure limit was derived from these calculations k1(infinite) = (3.2 +/- 0.7) x 10-12(T/298)-(1.2+/-0.4) cm3 molecule-1 s-1.All the parameters to be used in Troe's analytical expression for calculating the bimolecular rate constant at any pressure and temperature are given.The rate constant at the low-pressure limit k1(0) is more than an order of magnitude lower than for the CF3 radical.The RRKM calculations show that this arises from a large difference in the C-C bond dissociation energies in the corresponding peroxy radicals: 81.9 kJ mol-1 for CCl3O2 instead of ca. 145 kJ mol-1 for CF3O2.
Photocatalysis of chloroform decomposition by hexachloroosmate(IV)
Pena, Laura A.,Hoggard, Patrick E.
, p. 467 - 470 (2010)
Hexachloroosmate(IV) effectively catalyzes the photodecomposition of chloroform in aerated solutions. The decomposition products are consistent with a mechanism in which excited state OsCl62- reduces chloroform, rather than one involving photodissociation of chlorine atoms. Trace amounts of ethanol or water in the chloroform lead to photosubstitution to form OsCl5(EtOH)- or OsCl5(H2O) -, neither of which is photocatalytically active.
Synthesis of Decorated Carbon Structures with Encapsulated Components by Low-Voltage Electric Discharge Treatment
Bodrikov, I. V.,Pryakhina, V. I.,Titov, D. Yu.,Titov, E. Yu.,Vorotyntsev, A. V.
, p. 60 - 69 (2022/03/17)
Abstract: Polycondensation of complexes of chloromethanes with triphenylphosphine by the action of low-voltage electric discharges in the liquid phase gives nanosized solid products. The elemental composition involving the generation of element distribution maps (scanning electron microscopy–energy dispersive X?ray spectroscopy mapping) and the component composition (by direct evolved gas analysis–mass spectrometry) of the solid products have been studied. The elemental and component compositions of the result-ing structures vary widely depending on the chlorine content in the substrate and on the amount of triphenylphosphine taken. Thermal desorption analysis revealed abnormal behavior of HCl and benzene present in the solid products. In thermal desorption spectra, these components appear at an uncharacteristically high temperature. The observed anomaly in the behavior of HCl is due to HCl binding into a complex of the solid anion HCI-2 with triphenyl(chloromethyl)phosphonium chloride, which requires a relatively high temperature (up to 800 K) to decompose. The abnormal behavior of benzene is associated with its encapsulated state in nanostructures. The appearance of benzene begins at 650 K and continues up to temperatures above 1300?K.
Destruction of chemical warfare agent simulants by air and moisture stable metal NHC complexes
Weetman, Catherine,Notman, Stuart,Arnold, Polly L.
supporting information, p. 2568 - 2574 (2018/02/28)
The cooperative effect of both NHC and metal centre has been found to destroy chemical warfare agent (CWA) simulants. Choice of both the metal and NHC is key to these transformations as simple, monodentate N-heterocyclic carbenes in combination with silver or vanadium can promote stoichiometric destruction, whilst bidentate, aryloxide-tethered NHC complexes of silver and alkali metals promote breakdown under mild heating. Iron-NHC complexes generated in situ are competent catalysts for the destruction of each of the three targetted CWA simulants.
Photocatalytic Conversion of a FeCl3–CCl4–ROH System
Makhmutov
, p. 695 - 700 (2018/03/08)
The photocatalytic transformations of carbon tetrachloride and aliphatic primary alcohols in the presence of iron trichloride and a molar ratio of components FeCl3: CCl4: ROH = 1: 300: 2550 were studied. CCl4 is transformed into chloroform and hexachloroethane after exposure to a mercury lamp (250 W) to the FeCl3–CCl4–ROH system at 20°C, whereas the primary ROH alcohols are selectively oxidized into acetals (1,1-dialkoxyalkanes). The maximum conversion of CCl4 reaches 80%. The kinetics and mechanism of the photocatalytic conversion of the FeCl3–CCl4–ROH system are considered.
