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7647-01-0Relevant articles and documents
Catalytic Activity of Bismuth(III) Chloride for Dehydrochlorination of Poly(vinylchloride)
Uemichi, Yoshio,Takuma, Kazuhiko,Sugioka, Masatoshi,Kanazuka, Takaji
, p. 735 - 737 (1991)
Bismuth(III) chloride was found to be highly active as a catalyst for the dehydrochlorination of poly(vinylchloride).The degree of dehydrochlorination was 97percent at the highest.The catalyst showed high activity even in water vapor.
Kinetics of thermal dehydration and decomposition of Fe(III) chloride hydrate (FeCl3·xH2O)
Kanungo,Mishra
, p. 385 - 401 (1997)
Fe(III) chloride hydrate (FeCl3·xH2O) undergoes simultaneous dehydration and dehydrochlorination from its molten phase in the temperature range 100-200°C. The kinetics of these two parallel thermal processes has been studied by both isothermal and non-isothermal methods. Whereas for the dehydration reaction at temperature below 125°C a second order rate model (F2) fits well, a three-dimensional diffusion (D3) model is found to fit better at temperature above 135°C. For the dehydrochlorination reaction an interface growth controlled model of 1/3 order (F 1/3) appears to be the most suitable over a wide range of reaction. Dynamic thermogravimetry reveals two major steps in the temperature range 50-250°C. The first step which corresponds to the loss of about 4 mols of H2O, invariably follows second order kinetics (F2). The second step which is predominantly a process of dehydrochlorination, generally fits mixed diffusion controlled models due to the overlapping with the dehydration process. There is an excellent agreement in results among the isothermal and non-isothermal methods of determining kinetic parameters.
Thermal dehydration and decomposition of FeCl3·xH2O
Kanungo,Mishra
, p. 1487 - 1500 (1996)
Thermal dehydration and decomposition characteristics of Fe(III) chloride hydrate have been studied by both isothermal and non-isothermal methods. After the initial melting at 35-40°C both dehydration and decomposition of the salt proceed simultaneously at temperature above 100°C. At 250-30°C a stable hydrated Fe(OH)2Cl is formed representing the first plateau region in the TG curve. Around 400°C, a second plateau is observed corresponding to the formation of mostly Fe2O3 which however retains some OH groups and Cl- ions. However, these temperature ranges vary with the TA equipments used. Chemical analysis of the products of decomposition at temperatures above 140°C also gives evidence for the formation of FeOCl which on hydrolysis in water gives FeCl3 in solution. The FT-IR spectra suggest the presence of structural OH groups even for samples calcined at 300-400°C. The XRD patterns of the products of decomposition in the temperature range 160-400°C indicate the presence of β-FeOOH, some unidentified basic chlorides and α-Fe2O3.
Synthesis, solution and spectral studies of palladium(II) complexes with 2-hydroxyacetophenone N(3)-propylthiosemicarbazone. Crystal structure of a tripalladium complex
Yadav, Paras N.,Demertzis, Mavroudis A.,Kovala-Demertzi, Dimitra,Castineiras, Alfonso,West, Douglas X.
, p. 204 - 209 (2002)
The reactions of palladium(II) salts with 2-hydroxyacetophenone N(3)-propylthiosemicarbazone, H2Ap3Pr, are described. The synthesis and spectral characterization of a new triangular, trinuclear palladium(II) complex with the dianion, Ap3Pr2-, are reported. The X-ray crystal structure determination of [Pd(Ap3Pr2)]3·DMF shows it to contain a chair-form hexagon of alternating Pd and S atoms to form a molecular bowl. The spectrophotometric characterization of H2Ap3Pr is also reported.
Kinetic study of the reaction of chlorine atoms with dichloromethane and D-dichloromethane in the gas phase
Sarzyński, Dariusz,Gola, Agnieszka A.,Brudnik, Katarzyna,Jodkowski, Jerzy T.
, p. 220 - 225 (2011)
The kinetics of the gas-phase reactions of chlorine atoms with dichloromethane (CH2Cl2) and D-dichloromethane (CD 2Cl2) was studied using the relative rate method with Cl + CH3Br as the reference reaction. The rate constants for H-abstraction from CH2Cl2 (kH) and D-abstraction from CD2Cl2 (kD) were measured in the temperature range of 298-527 K and at a total pressure of 100 Torr using N2 as a diluent. The temperature dependencies of the rate constants (with the 2σ error limits) are described by the expressions: kH = (8.69 ± 0.82) × 10-12 × exp(-955 ± 20/T) and kD = (6.98 ± 0.91) × 10-12 × exp(-1285 ± 25/T) cm3 molecule-1 s-1. The kinetic isotope effect, described by the ratio kH/kD, was found of 3.8 ± 0.2 at room temperature.
Low-temperature structures of fac-trichloro(tetrahydrofuran)(D,L-tetrahydrofurfuranol)titanium(III) and fac-trichloro(tetrahydrofuran)(D,L-tetrahydrofurfuroxide)titanium(IV)
Olejnik, Zofia,Lis, Tadeusz,Utko, Jozef,Sobota, Piotr
, p. 847 - 850 (1996)
The title compounds, (I) [TiCl3(C5H10O2)(C4H 8O)] [IUPAC name: fac-trichloro(tetrahydrofuran)(D,L-tetrahydrofuran-2-methanol-O,O′) titanium(III)], and (II) [TiCl3(C5H
Tunable diode laser study of the reaction OH + ClO → HCl + O2
Tyndall,Kegley-Owen,Kegley-Owen,Orlando,Fried
, p. 1567 - 1575 (2002)
The main pathways for the formation of HCl in the stratosphere are through the reaction of chlorine atoms with methane and formaldehyde: Cl + CH4 → HCl + CH3. The production of HCl in the reaction of OH and ClO radicals was measured using time-resolved tunable diode laser spectroscopy. OH and ClO radicals were formed from the 308 nm laser photolysis of mixtures containing O3, Cl2, and H2O. The rate coefficient of 1.25 × 10-12 cc/molecule-sec for the reaction at 298 K was derived. This reaction rate corresponded to a branching fraction of 6.5% relative to the currently recommended rate coefficient for the overall reaction, indicating that the reaction has a significant impact on the partitioning of chlorine compounds in the stratosphere.
A Reinvestigation of the Laser-Initiated Cl2/HBr Chain Reaction: Absolute Rate Constants and the ν = 2/ν = 1 Ratio from Cl+HBrHCl(ν)+Br
Dolson, David A.,Leone, Stephen R.
, p. 3543 - 3550 (1987)
The Cl2/HBr chain reaction is reinvestigated by using real time state-selected observations of Δν = -1 chemiluminescence from the HCl(ν) products following pulsed laser photolysis of Cl2.These state-selected observation are analyzed with a more complete kinetic treatment to obtain room temperature rate constats for the chain propagation steps and the vibrational deactivation of HCl(ν=1,2) by HBr.The chain propagation rate constants are kR1=(1.02+/-0.15)E-11 and kR2=(1.1+/-0.4)E-15 cm3 molecule-1s-1, respectively , for Cl+HBrHCl(ν)+Br and Br+Cl2BrCl+Cl.Rate constants for vibrational deactivation of HCl(ν=1) and HCl(ν=2) by HBr are kV1=(1.06+/-0.16)E-12 and kV2=(2.09+/-0.50)E-12 cm3 molecule-1 s-1.Relative intensity measurements of the HCl ν=21 and 10 vibrational fluorescence are used to obtain an HCl(ν) product branching ratio, Nν=2/Nν=1=0.40+/-0.06.The kinetic analysis indicates that broad-band observations of infrared chemiluminescence may lead to erroneous rate constant determinations because of vibrational cascade, whereas the detection of the individual vibrational states leads to correct results.
Kinetic study of heterogeneous reaction of deliquesced NaCl particles with gaseous HNO3 using particle-on-substrate stagnation flow reactor approach
Liu,Cain,Wang,Laskin
, p. 10026 - 10043 (2007)
Heterogeneous reaction kinetics of gaseous nitric acid with deliquesced sodium chloride particles NaCl(aq) + HNO3(g) → NaNO 3(aq) + HCl(g) were investigated with a novel particle-on-substrate stagnation flow reactor (PS-SFR) approach under conditions, including particle size, relative humidity, and reaction time, directly relevant to the atmospheric chemistry of sea salt particles. Particles deposited onto aft electron microscopy grid substrate were exposed to the reacting gas at atmospheric pressure and room temperature by impingement via a stagnation flow inside the reactor. The reactor design and choice of flow parameters were guided by computational fluid dynamics to ensure uniformity of the diffusion flux to all particles undergoing reaction. The reaction kinetics was followed by observing chloride depletion in the particles by computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM/EDX). The validity of the current approach was examined first by conducting experiments with median dry particle diameter Dp = 0.82 μm, 80% relative humidity, particle loading densities 4 × 104 ≤ Ns ≤ 7 × 106 cm-2 and free stream HNO3 concentrations 2, 7, and 22 ppb. Upon deliquescence the droplet diameter D d approximately doubles. The apparent, pseudo-first-order rate constant determined in these experiments varied with particle loading and HNO3 concentration in a manner consistent with a diffusion-kinetic analysis reported earlier (Laskin, A.; Wang, H.; Robertson, W. H.; Cowin, J. P.; Ezell, M. J.; Finlayson-Pitts, B. J. J. Phys. Chem. A 2006, 110, 10619). The intrinsic, second-order rate constant was obtained as kII = 5.7 × 10-15 cm3 molecule-1 s-1 in the limit of zero particle loading and by assuming that the substrate is inert to HNO3. Under this loading condition the experimental, net reaction uptake coefficient was found to be γnet = 0.11 with an uncertainty factor of 3. Additional experiments examined the variations of HNO3 uptake on pure NaCl, a sea salt-like mixture of NaCl and MgCl2 (Mg-to-Cl molar ratio of 0.114) and real sea salt particles as a function of relative humidity. Results show behavior of the uptake coefficient to be similar for all three types of salt particles with Dp ～ 0.9 μm over the relative humidity range 20-80%. Gaseous HNO3 uptake coefficient peaks around a relative humidity of 55%, with γnet well over 0.2 for sea salt. Below the efflorescence relative humidity the uptake coefficient declines with decreasing RH for all three sea salt types, and it does so without exhibiting a sudden shutoff of reactivity. The uptake of HNO3 on sea salt particles was more rapid than that on the mixture of NaCl and MgCl2, and uptake on both sea salt and sea salt-like mixture was faster than on pure NaCl. The uptake of HNO3 on deliquesced, pure NaCl particles was also examined over the particle size range of 0.57 ≤ Dp ≤ 1.7 μm (1.1 ≤ Dd ≤ 3.4 μm) under a constant relative humidity of 80%. The uptake coefficient decreases monotonically with an increase in particle size. Application of a resistance model of reaction kinetics and reactant diffusion over a single particle suggests that, over the range of particle size studied, the uptake is largely controlled by gaseous reactant diffusion from the free stream to the particle surface. In addition, a combined consideration of uptake coefficients obtained in the present study and those previously reported for substantially smaller droplets (Dd ～ 0.1 μm) (Saul, T. D.; Tolocka, M. P.; Johnston, M. V. J. Phys. Chem. A 2006, 110, 7614) suggests that the peak reactivity occurs at a droplet diameter of ～0.7 μm, which is immediately below the size at which sea salt aerosols begin to notably contribute to light scattering.
Reaction Process of Titanium Tetrachloride with Ammonia in the Vapor Phase and Properties of the Titanium Nitride Formed
Saeki, Yuzo,Matsuzaki, Ryoko,Yajima, Akimasa,Akiyama, Masayo
, p. 3193 - 3196 (1982)
The reaction products of gaseous TiCl4 with ammonia were TiCl4*5NH3 at 200 deg C, TiCl4*5NH3, TiClN, and NH4Cl at 250-400 deg C, TiCl4*5NH3, TiClN, TiNx, and NH4Cl at 450-650 deg C, TiNx and NH4Cl at 700-1000 deg C, and TiNx, NH4Cl, and HCl at 1100-1400 d