scholarly journals Kinetics of the Addition Reactions of Thiobenzoic Acids to Styrenes or Ethynylbenzenes as the Model of Polyaddition. Study on the Rate-Determining Step and Substituent Effect

1993 ◽  
Vol 25 (5) ◽  
pp. 507-520 ◽  
Author(s):  
Eiichi Kobayashi ◽  
Masaki Sakakibara ◽  
Takatsugu Obata ◽  
Sadahito Aoshima ◽  
Junji Furukawa
Keyword(s):  
Substituent Effect ◽  
Addition Reactions ◽  
Rate Determining Step ◽  
Kinetics Of

Ionic dimerisation of trifluoropropenenitrile and its addition reactions with methyl trifluoropropenoate

1980 ◽  
Vol 45 (2) ◽  
pp. 406-414 ◽  
Author(s):  
Jiří Svoboda ◽  
Oldřich Paleta ◽  
Václav Dědek
Keyword(s):  
Reaction Mechanism ◽  
Proton Transfer ◽  
Substituent Effect ◽  
Solvent Molecule ◽  
Addition Product ◽  
Potassium Fluoride ◽  
Relative Reactivity ◽  
Addition Reactions ◽  
Tertiary Amines ◽  
Optimum Conditions

Dimerisation of trifluoropropenenitrile (I) in the presence of potassium fluoride and tertiary amines afforded a mixture of stereoisomeric perfluoro-4-methyl-pentenedinitriles (II), higher-boiling compounds, and 2,3,3,3-tetrafluoropropanenitrile (III) which arises by proton transfer from the solvent molecule. Under optimum conditions, product II was obtained in about 50% yield. Reaction of the nitrile I with methyl trifluoropropenoate (IV) gave, besides the dimers II and V, the product of addition of the nitrile I to the propenoate, IV, i.e. methyl 4-cyanoperfluoro-2-pentenoate (VI), and the addition product of the propenoate IV to the nitrile I, i.e. methyl 4-cyanoperfluoro-2-methyl-3-butenoate (VII). The relative reactivity if I and IV is discussed. The ratio of stereoisomers in II, V, VI and VII indicates that the magnitude of the steric substituent effect, operating in the reaction mechanism, decreases in the order -CFCF3.(COOCH3) > -CFCF3(CN) > -COOCH3 > -CN.

Kinetics of carbon monoxide methanation on a Ni/SiO2 catalyst

1990 ◽  
Vol 55 (7) ◽  
pp. 1678-1685
Author(s):  
Vladimír Stuchlý ◽  
Karel Klusáček
Keyword(s):  
Carbon Monoxide ◽  
Reaction Rate ◽  
Catalyst Activity ◽  
Adsorbed Hydrogen ◽  
Reaction Products ◽  
Co Methanation ◽  
Molar Ratios ◽  
Rate Determining Step ◽  
Higher Temperature ◽  
Kinetics Of

Kinetics of CO methanation on a commercial Ni/SiO2 catalyst was evaluated at atmospheric pressure, between 528 and 550 K and for hydrogen to carbon monoxide molar ratios ranging from 3 : 1 to 200 : 1. The effect of reaction products on the reaction rate was also examined. Below 550 K, only methane was selectively formed. Above this temperature, the formation of carbon dioxide was also observed. The experimental data could be described by two modified Langmuir-Hinshelwood kinetic models, based on hydrogenation of surface CO by molecularly or by dissociatively adsorbed hydrogen in the rate-determining step. Water reversibly lowered catalyst activity and its effect was more pronounced at higher temperature.

scholarly journals Single entity electrochemistry and the electron transfer kinetics of hydrazine oxidation

Nano Research ◽  
2021 ◽  
Author(s):  
Ruiyang Miao ◽  
Lidong Shao ◽  
Richard G. Compton
Keyword(s):  
Electron Transfer ◽  
Bulk Solution ◽  
Relative Contribution ◽  
Rate Determining Step ◽  
Multistep Process ◽  
Ph Range ◽  
Electro Catalytic Oxidation ◽  
Single Particle Impact ◽  
The Impact ◽  
Kinetics Of

AbstractThe mechanism and kinetics of the electro-catalytic oxidation of hydrazine by graphene oxide platelets randomly decorated with palladium nanoparticles are deduced using single particle impact electrochemical measurements in buffered aqueous solutions across the pH range 2–11. Both hydrazine, N2H4, and protonated hydrazine N2H5+ are shown to be electroactive following Butler-Volmer kinetics, of which the relative contribution is strongly pH-dependent. The negligible interconversion between N2H4 and N2H5+ due to the sufficiently short timescale of the impact voltammetry, allows the analysis of the two electron transfer rates from impact signals thus reflecting the composition of the bulk solution at the pH in question. In this way the rate determining step in the oxidation of each specie is deduced to be a one electron step in which no protons are released and so likely corresponds to the initial formation of a very short-lived radical cation either in solution or adsorbed on the platelet. Overall the work establishes a generic method for the elucidation of the rate determining electron transfer in a multistep process free from any complexity imposed by preceding or following chemical reactions which occur on the timescale of conventional voltammetry.

scholarly journals The kinetics of the hydrogen chloride oxidation

2013 ◽  
Vol 78 (12) ◽  
pp. 2115-2130 ◽  
Author(s):  
Martinez Gonzalez ◽  
Tanja Vidakovic-Koch ◽  
Rafael Kuwertz ◽  
Ulrich Kunz ◽  
Thomas Turek ◽  
...  
Keyword(s):  
Kinetic Parameters ◽  
Gas Phase ◽  
Hydrogen Chloride ◽  
Reaction Order ◽  
Membrane Electrode ◽  
Polarization Data ◽  
Rate Determining Step ◽  
Electrode Assemblies ◽  
Apparent Kinetic Parameters ◽  
Kinetics Of

Hydrogen chloride (HCl) oxidation has been investigated on technical membrane electrode assemblies in a cyclone flow cell. Influence of Nafion loading, temperature and hydrogen chloride mole fraction in the gas phase has been studied. The apparent kinetic parameters like reaction order with respect to HCl, Tafel slope and activation energy have been determined from polarization data. The apparent kinetic parameters suggest that the recombination of adsorbed Cl intermediate is the rate determining step.

scholarly journals A Labile Metallo-Porphyrin as Tool to Control J-Aggregates Chiroptical Properties

2020 ◽  
Author(s):  
Luigi Monsù Scolaro ◽  
Ilaria Occhiuto ◽  
Mariachiara Trapani ◽  
ROBERTO ZAGAMI ◽  
Andrea Romeo ◽  
...  
Keyword(s):  
Dipolar Coupling ◽  
Initial Conditions ◽  
Coupling Mechanism ◽  
Precise Control ◽  
Rate Determining Step ◽  
Initial Nucleus ◽  
Acidic Conditions ◽  
J Aggregates ◽  
Kinetics Of ◽  
Autocatalytic Growth

The zinc(II) metal derivative of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4) is quite labile and readily demetallates under acidic conditions, affording the parent diacid porphyrin in a monomeric form. The rate of this process is first order on [ZnTPPS4] and second order on [H+], allowing a precise control of the monomer release in solution. Under high ionic strength, this latter species is able to self-assemble into J-aggregates, whose kinetics of growth are largely modulated by pH. The aggregation kinetics have been treated according to a well-established model, in which the formation of an initial nucleus is the rate determining step preceding the autocatalytic growth of the whole assembly. The extinction spectra of the aggregates suggest the occurrence of a dipolar coupling mechanism very similar to that operating in metal nanoparticles. Spontaneous symmetry breaking takes place in these aggregates as evidenced by unusual circular dichroism spectra. The intensity and sign of the effect is controlled by the aggregation rate and therefore can be tuned through a proper choice of initial conditions.

Kinetics of H abstraction and addition reactions of 2,4,4-trimethyl-1-pentene by OH radical

Fuel ◽  
2017 ◽  
Vol 210 ◽  
pp. 646-658 ◽  
Author(s):  
Geyuan Yin ◽  
Erjiang Hu ◽  
Feiyu Yang ◽  
Jinfeng Ku ◽  
Zuohua Huang
Keyword(s):  
Addition Reactions ◽  
Oh Radical ◽  
Kinetics Of

scholarly journals Understanding the unexpected effect of frequency on the kinetics of a covalent reaction under ball-milling conditions

2019 ◽  
Vol 15 ◽  
pp. 1226-1235 ◽  
Author(s):  
Ana M Belenguer ◽  
Adam A L Michalchuk ◽  
Giulio I Lampronti ◽  
Jeremy K M Sanders
Keyword(s):  
Crystal Size ◽  
Crystal Surface ◽  
Onset Time ◽  
Initial Energy ◽  
Crystal Defects ◽  
Exponential Dependence ◽  
Disulfide Exchange ◽  
Rate Determining Step ◽  
Local Defects ◽  
Kinetics Of

We here explore how ball-mill-grinding frequency affects the kinetics of a disulfide exchange reaction. Our kinetic data show that the reaction progress is similar at all the frequencies studied (15–30 Hz), including a significant induction time before the nucleation and growth process starts. This indicates that to start the reaction an initial energy accumulation is necessary. Other than mixing, the energy supplied by the mechanical treatment has two effects: (i) reducing the crystal size and (ii) creating defects in the structure. The crystal-breaking process is likely to be dominant at first becoming less important later in the process when the energy supplied is stored at the molecular level as local crystal defects. This accumulation is taken here to be the rate-determining step. We suggest that the local defects accumulate preferentially at or near the crystal surface. Since the total area increases exponentially when the crystal size is reduced by the crystal-breaking process, this can further explain the exponential dependence of the onset time on the milling frequency.

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