Search results for " rate constant"
showing 10 items of 220 documents
Dissociation energies of silver clusters Agn+, n=14, 15, 16, 18
2003
A recently developed method to determine dissociation energies has been applied to positively charged silver clusters of size n=14, 15, 16 and 18. The method uses a combination of sequential and single step decays. It requires an uncalibrated thermometer which here is provided by the evaporation rate constants of the product clusters. For this purpose, earlier measurements [J. Chem. Phys. 57 (1998) 2786] are reanalyzed with the new method. The resulting dissociation energies are compared with the liquid drop values and the measured decay rate constants with expected rate constants from detailed balance theory.
Ein modell zur beschreibung bimolekularer reaktionen zwischen reaktiven gruppen, die in zwei polymerknäuel eingebaut sind
1968
Die Beobachtung, das die Geschwindigkeitskonstante des Kettenabbruchs bel der radikalischen Polymerisation des Methylmethacrylats umgekehrt proportional der Viskositat des Losungsmittels und vollig unabhangig vom Molekulargewicht ist, wird durch folgendes Modell erklart: 1. Die Polymerknauel behindern nicht ihre gegenseitigen Bewegungen und konnen sich bei einer Begegnung vollstandig durchdringen (Unabhangigkeit der Selbstdiffusionskonstante von der Konzentration). 2. Die Reaktion findet im Uberlappungsraum zweier sich begegnender Polymerradikale wahrend der Begegnungsdauer τ statt. Eine statistische Rechnung zeigt, das unter dieser Annahme die gemessene bimolekulare Geschwindigkeitskonstan…
Kinetics of the formation reactions of trichloro- and tribromomethyl hypohalites and alcohols in the gas-phase: Theoretical study
2007
Abstract The CX3OY molecules (X = Cl, Br and Y = H, F, Cl, Br) can be formed in the atmosphere by the recombination CX3 + OY and CX3O + Y reactions. In the present study the results of a theoretical analysis of the kinetics and thermochemistry of this class of reactions are performed. The molecular properties of the reactants and products were derived from ab initio calculations. The high-pressure limiting rate constants for the recombination reactions were evaluated using a version of the statistical adiabatic channel model. The kinetic equations derived in this study allow a description of the kinetics of the reactions under investigation in the temperature range of 200–400 K.
The influence of internal degrees of freedom on the unimolecular decay of the molecule–cluster compound Au8+CH3OH
2002
Time-resolved photodissociation measurements of the sequential reaction Au8+CH3OH→Au8+→Au7+ and the direct reaction Au8+→Au7+ have been performed for several excitation energies. The production rates and yields of the final state Au7+ in the sequential process are strongly influenced by the excitation energy deposited into the evaporated methanol molecule during the initial fragmentation step. Both the rate constants and yields can be fitted with a single parameter, the cluster–methanol binding energy.
Quantum Dynamics of the 18O + 36O2 Collision Process
2015
We report full quantum cross sections and rate constants for the (18)O + (36)O2 → (36)O2 + (18)O collision process. This constitutes to the best of our knowledge the first dynamical study of the (18)O(18)O(18)O system, with three identical (18)O oxygen atoms. We emphasize the comparison with the (16)O + (32)O2 collision as this latter presents the exact same features as the one treated here, except the consistent change of mass for all three atoms. We find very similar behaviors in the cross sections, and we confirm that the rates are faster when three identical nuclei are involved. In particular, we cannot dynamically study this system with classical trajectory methods, and we have to incl…
Facile approaches to build ordered amphiphilic tris(phthalocyaninato) europium triple-decker complex thin films and their comparative performances in…
2010
Solution processed thin films of an amphiphilic tris(phthalocyaninato) rare earth triple-decker complex, Eu(2)[Pc(15C5)(4)](2)[Pc(OC(10)H(21))(8)], have been prepared from three different methods: self-assembly (SA) annealed in solvent vapor, quasi-Langmuir-Shäfer (QLS) and drop casting methods. In particular, we successfully developed a simple QLS process for fabricating ordered multilayers with a good thickness control. The films prepared from three different methods were characterized by a wide range of methods including electronic absorption spectra, IR, X-ray diffraction, atomic force microscopy (AFM), and current-voltage (I-V) measurements. J-type aggregates have been formed with the …
A study of the mechanism of the oxidative cyclization of benzaldehyde semicarbazones induced by cupric perchlorate in acetonitrile
1995
Treatment of benzaldehyde semicarbazones 1a-i with cupric perchlorate in acetonitrile at 40 provided selectively the corresponding 1,2,4-triazolin-5-ones 2a-i. The relative rate constants for 2a-i formation were determined by the competitive method. The results obtained showed that electron-donating substituents (methyl and methoxy) increase the reaction rate, while the reverse was found for electron-withdrawing substituents (chloro and nitro group). The reactivity data are discussed on the grounds of two possible mechanisms.
Kinetik der Bromierung von Phenolen und phenolischen Mehrkernverbindungen, 1. Mechanismus und meßmethode
1975
Die Bromierung von 2-(2-Hydroxy-5-methylbenzyl)-4,6-dimethylphenol (1) und 2-[2-Hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylbenzyl]-4,6-dimethylphenol (2a) wurde in Eisessig bei 22°C untersucht. Die Reaktion last sich fur [Br2]0 = 1,4·10−3 bis 6,0·10−3 mol dm + und Konzentrationen der phenolischen Verbindungen [P]0 zwischen 1,1·10−3 und 5,5·10−3mol dm−3 durch das folgende Geschwindigkeitsgesetz beschreiben: Wahrend die gebildete Bromverbindung keinen Einflus auf die Reaktionsgeschwindigkeit hat, verlangsamt der entstehende Bromwasserstoff die Reaktion. Die Bromierung ist trotzdem zur Bestimmung der Reaktionsfahigkeit von Phenolen und phenolischen Mehrkernverbindungen gut geeignet, da die R…
Rate-retarding effects of mixed anionic/non-ionic micelles on the alkaline hydrolysis of the chloropentamminocobalt(III) complex
2006
Abstract Rate data for the alkaline hydrolysis of the chloropentaamminecobalt(III) cation in the presence of mixed micelles composed of (i) anionic sodium decylsulphate (SDeS) and non-ionic dodecylpenta(oxyethylene glycol) monoether (C 12 E 5 ) surfactants and (ii) anionic sodium perfluorooctanoate (SPFO) and non-ionic C 12 E 5 surfactants has been obtained at T 298 K and constant electrolyte concentration 0.08 mol dm −3 ([NaOH] = 0.01 mol dm −3 , [NaClO 4 ] = 0.07 mol dm −3 ) over a wide range of total surfactant concentration ( C t ) and anionic mole fraction ( χ ). The critical micelle concentrations (c.m.c.s) of the mixed micelles have been determined over the entire χ range by means of…
Radikalpolymerisation von methylmethacrylat im gesamten umsatzbereich. Stationäre und instationäre experimente zur bestimmung von wachstums- und abbr…
1989
Free-radical polymerization of methyl methacrylate in bulk at 0°C over the full range of conversion is reported. Details for stationary and non-stationary experiments are described allowing to measure both kinetically relevant ratios fk/ka and kw/ka, f representing radical efficiency, kw rate constants of propagation and ka rate constant of termination. From these ratios the absolute rate constants kw and ka are available. The photochemical decay of the initiator 1,1′-azodicyclohexanenitrile in connection with the rotating-sector technique and observation of the post-effect after stopping the initiator decay were used. The rate of polymerization and the number- and weight-average molar mass…