7790-93-4Relevant articles and documents
Crystal structure and characterization of L-arginine chlorate and L-arginine bromate
Petrosyan,Karapetyan,Sukiasyan,Aghajanyan,Morgunov,Kravchenko,Bush
, p. 144 - 152 (2007/10/03)
The salts L-arginine.HClO3 and L-arginine.HBrO3, were synthesized. The crystals obtained were characterized by IR and NQR spectroscopy, thermal analysis, Nd:YAG laser radiation second harmonic generation, dielectric, piezoelectric an
New pathways for chlorine dioxide decomposition in basic solution
Odeh, Ihab N.,Francisco, Joseph S.,Margerum, Dale W.
, p. 6500 - 6506 (2008/10/08)
The product distribution from the decay of chlorine dioxide in basic solution changes as the ClO2 concentration decreases. While disproportionation reactions that give equal amounts of ClO2- and ClO3- dominate the stoichiometry at millimolar or higher levels of ClO2, the ratio of ClO2- to ClO3- formed increases significantly at micromolar ClO2 levels. Kinetic evidence shows three concurrent pathways that all exhibit a first-order dependence in [OH-] but have variable order in [ClO2]. Pathway 1 is a disproportionation reaction that is first order in [ClO2]. Pathway 2, a previously unknown reaction, is also first order in [ClO2] but forms ClO2- as the only chlorine-containing product. Pathway 3 is second order in [ClO2] and generates equal amounts of ClO2- and ClO3-. A Cl2O4 intermediate is proposed for this path. At high concentrations of ClO2, pathway 3 causes the overall ClO3- yield to approach the overall yield of ClO2-. Pathway 2 is attributed to OH- attack on an oxygen atom of ClO2 that leads to peroxide intermediates and yields ClO2- and O2 as products. This pathway is important at low levels of ClO2.
Properties of dichlorine hexaoxide in the gas phase and in low-temperature matrices
Jansen, Martin,Schatte, Gabriele,Tobias, Klaus M.,Willner, Helge
, p. 1703 - 1706 (2008/10/08)
The IR spectrum of matrix-isqlated dichlorine hexaoxide shows that there are two inequivalent chlorine atoms in the molecule and that it is best described as the mixed anhydride of chloric and perchloric acids. Of 18 fundamental vibrations, 16 were observed and many of them were assigned. O3ClOClO2 exhibits a broad UV absorption at 268 nm (εmax = 3000 dm3 mol-1 cm-1) in the gas phase. It is decomposed on photolysis in an Ar matrix to ClOClO3 and O2. The kinetics of formation and decomposition of O3ClOClO2 in the gas phase were also investigated. The rate of formation depends strongly on the concentration of ClO2 and O3. Cl2O6 does not dissociate into ClO3 radicals, and the primary stable decomposition products are ClO2, ClOClO3, and O2.
Kinetics and Mechanism of the Reaction between Chlorine(III) and Bromide Ion
Valdes-Aguilera, Oscar,Boyd, Donald W.,Epstein, Irving R.,Kustin, Kenneth
, p. 6702 - 6708 (2007/10/02)
The stoichiometry and kinetics of the reaction between chlorine(III) and bromide ion were studied spectrophotometrically at 25.0 +/- 0.5 deg C and ionic strength 1.2 M (NaClO4).The main products are Br3- and Cl- when bromide ion is in excess, ClO2 and Br2 when chlorine(III) is in excess.With sufficient acid and excess bromide ion, the stoichiometry of the reaction is HClO2 + 6Br- + 3H+ -> 2Br3- + Cl- +2H2O.The rate law for this reaction is (1/2)d->/dt = k+>-> where k = (9.51 +/- 0.14) * 10-2 s-1.When the reaction is carried out with > ->, the stoichiometry is difficult to define.In the range ca.= (1.50-2.00) * 10-3 M, -> ca.= 5.00 * 10-4 M, and ca.=0.20 M, a clock reaction occurs, the lag time of which decreases with addition of small amounts (-4 M) of molecular bromine.The complex rate law for the chlorine(III)-bromide ion reaction with excess Cl(III) can be explained by a 16-step mechanism including oxidation of bromide ion to bromine by chlorine(III), reduction of bromine to bromide ion, and decomposition of chlorous acid.A reduced set of 10 reactions and associated rate and equilibrium constants successfully modeled the clock reaction by computer simulation.
ETUDE ET CARACTERISATION PAR SPECTROMETRIE INFRAROUGE DES OXYDES DE CHLORE, (ClO)2, ClO2, Cl2O4 et Cl2O3, FORMES DANS LES INTERACTIONS CHLORE-OZONE
Loupec, R. C.,Potier, J.
, p. 449 - 454 (2007/10/02)
The non photochemical reaction of (O2 + O3) (9) with Cl2 (1) at -78, -44, -40 deg C essentially gives chlorine chlorate which is characterized by ν(ClOCl) at 785 and 745 cm-1.Water traces lead to ClO2 but also to HClO3, HCl and to small quantities of other chlorine oxydes by a water catalyzed process.In the darkness and in the gas phase (p = 3 atm and t = 15 deg C) pure ozone reacts with chlorine and gives a ClO2 rich mixture containing also a high proportion of chlorine clorate with chlorine perchlorate traces; chlorine chlorate is characterized by νs(ClO2) = 1015 cm-1 νas(ClO2) = 1280 cm-1 and the two bridge vibrations νClOCl at 735 and 695 cm-1.Reactional mechanisms are proposed.Keywords: Ozone chlorine, chlorine chlorite, chlorine chlorate, chlorine perchlorate, chloric acid, I.R. spectroscopy.
Disproportionation of chlorous acid. I. Stoichiometry
Kieffer, Robert G.,Gordon, Gilbert
, p. 235 - 239 (2008/10/08)
The disproportionation of chlorous acid was studied at an ionic strength of 2.0 M under a variety of hydrogen ion conditions from 1.2 × 10-3 to 2.0 M and with up to 0.1 M added chloride ion. In the absence of added chloride ion, in 1.2 and 2.0 M perchloric acid at 25°, the stoichiometry can be approximated as: 4HClO2 → 2ClO2 + ClO3- + Cl- + 2H+ + H2O. At the beginning of the reaction less chlorine dioxide than that predicted by the above equation is formed, and, as the reaction proceeds, the relative amount of chlorine dioxide produced increases. The relative amount of chlorine dioxide produced also varies with the hydrogen ion concentration. Chloride ion catalyzes the disproportionation of chlorous acid and also alters the stoichiometry to approximately 5HClO2 → 4ClO2 + Cl- + H+ + 2H2O. As the reaction proceeds in the presence of initial chloride ion, less chlorine dioxide than that predicted by the second equation is formed. Also, as the initial concentration of chloride ion is decreased, the relative amount of chlorine dioxide formed decreases. A mechanism which is consistent with these observations is proposed.
