Search results for "reaction rate constant"
showing 10 items of 210 documents
Properties of trialkylamines as catalysts of resoles synthesis
2000
A series of the syntheses of phenol–formaldehyde resoles was carried out in the presence of trimethyl-, triethyl-, tripropyl-, and tributylamines and sodium hydroxide as catalysts for this process. The rate constants were calculated for the partial reactions identified in the synthesis. Also, the performance properties of the resins obtained and the hardened resin samples were estimated in simple tests. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 898–902, 2000
Electronic Excitation Energy Transfer in Multichromophoric Assemblies: A Single Molecule Insight
2009
In recent years, single molecule spectroscopy has provided novel insights into the fundamentals of electronic excitation energy transfer in molecular aggregates. In order of increasing structural complexity, we have studied simple molecular dimers and multichromophoric dendrimers. It will be shown that the combination of frequency-selective single molecule spectroscopy and confocal fluorescence microscopy at 1.4 K is a unique tool to study energy transfer processes in these systems. In particular, from the line widths of single molecule excitation spectra, rate constants of energy transfer can be deduced directly. A detailed analysis shows that, for several cases, the mechanism of energy tr…
Nachweis des di-2-cyanoisopropylperoxides bei der zersetzung von azoisobuttersäuredinitril in gegenwart von sauerstoff
1970
Das Di-2-cyanoisopropylperoxid entsteht in etwa 5-proz. Ausbeute bei der Zersetzung von Azoisobuttersaredinitril unter Sauerstoff in Isobutyronitril als Losungsmittel. Thermisch zerfallt das Peroxid est oberhalb von 120°C mit mesbarer Geschwindigkeit in einer Reaktion erster Ordnung. Die Aktivierungsenergie, in Cumol als Losungsmittel, wurde zu 37,9 kcal · mol−1 bestimmt. Werte fur die Zerfallskonstante bei 140°C sind in Cumol 0,057 h−1, in tert-Butylbenzol 0,073 h−1, in Chlorbenzol 0,18 h−1 und in o-Dichlorbenzol 0,23 h−1. Di-2-cyanoisopropylperoxide is formed when azobisisobutyronitrile is decomposed under oxygen in isobutyronitrile as a solvent. The yield amounts to ca. 5%. Thermal decom…
Response ofBacillus subtilis spores to dehydration and UV irradiation at extremely low temperatures
1996
Spores of Bacillus subtilis have been exposed to the conditions of extreme dehydration (argon/silica gel; simulated space vacuum) for up to 12 weeks at 298 K and 80 K in the dark. The inactivation has been correlated with the production of DNA-double strand-breaks. The temperature-dependence of the rate constants for inactivation or production of DNA-double strand-breaks is surprisingly low. Controls kept in the frozen state at 250 K for the same period of time showed no sign of deterioration. In another series of experiments the spores have been UV irradiated (253.7 nm) at 298 K, 200 K and 80 K after exposure to dehydrating conditions for 3 days. Fluence-effect relationships for inactivati…
Powder X-Ray Diffraction Investigation of Xylazine Hydrochloride Solid Phase Transformation Kinetics
2013
The kinetics of the solid-state phase transformation of xylazine hydrochloride form X to A has been investigated using powder X-ray diffraction and differential thermal analysis. Three different kinetic models have been used to describe transition kinetics: the Avrami–Erofeev equation, the Cardew equation, and the methodology for simulation of solid-state phase transition kinetics by the combination of nucleation and nuclei growth processes. The latter has been recently developed and has been tested in this paper for the case of a real solid-state transition. The relative humidity, mechanical pressure, temperature, and sample-preparation effect on phase-transition kinetics have been investi…
The reduction mechanism of the CO group.
2001
A detailed study of the electrochemical reduction of benzil in aqueous medium between H0=−5 and pH 11 is presented. A global 2e−, 3H+ or 2e−, 2H+ surface reaction leads to cis and trans endiols. Analysis, using the theory of the square schemes with protonations at equilibrium, shows that in all the pH range the reaction is controlled by the second electron uptake, the paths being successively H+, e− and e−, H+. The electrochemical reaction is followed by surface isomerizations whose rate constants vary from 7 to 200 s−1 for the trans/cis and from 1 to 2000 s−1 for the cis/trans transformations.
Zur kinetik der anionischen polymerisation von methyl-methyacrylat in tetrahydrofuran bei −75°C
1973
Die anionische Polymerisation von Methylmethacrylat (MMA) in Tetrahydrofuran (THF) verlauft bei −75°C mit Cumylcasium bzw. oligomerem α-Methylstyrylcasium als Initiatoren ohne erkennbare Nebenreaktionen analog der anionischen Polymerisation von unpolaren Monomeren in atherischen Losungsmitteln. Als Beweis wird hauptsachlich die enge Molekulargewichtsverteilung der unter diesen Bedingungen hergestellten Polymethylmethacrylate angefuhrt. Bei −75°C betragen die Geschwindigkeitskonstanten fur die Monomeranlagerung an das Ionenpaar kw(±) = 80 dm3 mol−1 s−1 und an das freie Anion etwa kw(−) ≈ 6 · 104 dm3 mol−1 s−1. Leitfahigkeitsmessungen ergeben, das die Dissoziationskonstante des Polymethylmeth…
The reaction of 2-methoxy-3-nitrothiophene with N-benzylmethylamine in methanol
1990
The kinetics of the title reaction has been studied in methanol as a function of amine and methoxide ion concentrations. The kinetic coefficients obtained point out that the reaction is catalysed by methoxide through a SB catalysis mechanism.
Photophysical Properties of Charged Cyclometalated Ir(III) Complexes: A Joint Theoretical and Experimental Study
2011
The photophysical properties of a series of charged biscyclometalated [Ir(ppy)(2)(N boolean AND N)](1+) complexes, where ppyH is 2-phenylpyridine and N boolean AND N is 2,2'-bipyridine (bpy), 6-phenyl-2,2'-bipyridine (pbpy), and 6,6'-dipheny1-2,2'-bipyridine (dpbpy) for complexes 1, 2, and 3, respectively, have been investigated in detail. The photoluminescence performance in solution decreases from 1 to 3 upon attachment of phenyl groups to the ancillary ligand. The absorption spectra recorded over time suggest that complex 3 is less stable compared to complexes 1 and 2 likely due to a nucleophilic-assisted ancillary ligand-exchange reaction. To clarify this behavior, the temperature depen…
Electrochemical reduction and carboxylation of halobenzophenones
2002
Abstract The electrochemical reduction of a series of halogenated benzophenones XC6H4COC6H4Y (1) was studied in aprotic solvents, in the absence and presence of CO2, by cyclic voltammetry (CV) and controlled-potential electrolysis. The mechanism of electroreduction in dimethylformamide (DMF) has been investigated in some detail. Most of the compounds undergo reductive carbonhalogen bond cleavage in the time window of CV. The radical anions derived from difluorobenzophenones (X=Y=4-F; X=2-F, Y=4-F) as well as from the 3-chloro derivative are quite stable with a cleavage rate constant (kc) of the order of 10−2 s−1 or less. With 4-chloro-, 2-chloro-, 4,4′-dichloro- and 2,4′-dichorobenzophen…