Hydrogenation of alkenes on a nickel-tungsten-alumina catalyst

1981 ◽  
Vol 46 (9) ◽  
pp. 2076-2082 ◽  
Author(s):  
Jan Uchytil ◽  
Eva Kočová ◽  
Miloš Kraus
Keyword(s):  
Molecular Weight ◽  
Rate Constants ◽  
The Other ◽  
Alumina Catalyst ◽  
Boiling Points ◽  
Kinetics Of ◽  
Best Fit ◽  
Nickel Tungsten

Eleven C2 to C8 alkenes were hydrogenated on a reduced sulphided industrial nickel-tungsten catalyst. Kinetics of the reaction was investigated in detail for ethylene and data were correlated by different equations. Best fit was obtained by three equations of the Langmuir-Hinshelwood type and these were used to describe hydrogenation of the other alkenes. Logarithms of the rate constants obtained were correlated linearly with the sum of steric constants E0s of substituents of semihydrogenated state R1R2R3C-*. Also adsorption coefficients of alkenes were structure dependent, increased with molecular weight of alkene and correlated roughly with boiling points.

Benzhydrylium and tritylium ions: complementary probes for examining ambident nucleophiles

2015 ◽  
Vol 87 (4) ◽  
pp. 341-351 ◽  
Author(s):  
Armin R. Ofial
Keyword(s):  
Free Energy ◽  
Rate Constants ◽  
The Other ◽  
Steric Effects ◽  
Linear Free Energy Relationship ◽  
Reliable Tool ◽  
Linear Free Energy ◽  
Sensitivity Parameter ◽  
Meldrum's Acids ◽  
Kinetics Of

AbstractThe linear free energy relationship log k = sN(N + E) (eq. 1), in which E is an electrophilicity, N is a nucleophilicity, and sN is a nucleophile-dependent sensitivity parameter, is a reliable tool for predicting rate constants of bimolecular electrophile-nucleophile combinations. Nucleophilicity scales that are based on eq. (1) rely on a set of structurally similar benzhydrylium ions (Ar2CH+) as reference electrophiles. As steric effects are not explicitely considered, eq. (1) cannot unrestrictedly be employed for reactions of bulky substrates. Since, on the other hand, the reactions of tritylium ions (Ar3C+) with hydride donors, alcohols, and amines were found to follow eq. (1), tritylium ions turned out to be complementary tools for probing organic reactivity. Kinetics of the reactions of Ar3C+ with π-nucleophiles (olefins), n-nucleophiles (amines, alcohols, water), hydride donors and ambident nucleophiles, such as the anions of 5-substituted Meldrum’s acids, are discussed to analyze the applicability of tritylium ions as reference electrophiles.

THE REACTION OF 2,2-DIPHENYL-1-PICRYLHYDRAZYL WITH SECONDARY AMINES

1958 ◽  
Vol 36 (12) ◽  
pp. 1729-1734 ◽  
Author(s):  
J. E. Hazell ◽  
K. E. Russell
Keyword(s):  
Secondary Amine ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
Hydrogen Abstraction ◽  
Activation Energies ◽  
Major Product ◽  
The Other ◽  
Secondary Amines ◽  
First Order ◽  
Kinetics Of

The reaction of DPPH (2,2-diphenyl-1-picrylhydrazyl) with N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, diphenylamine, and methylaniline has been studied and has been shown to be primarily a hydrogen abstraction process. Two moles DPPH react with 1–1.15 moles secondary amine to give 1.7–1.8 moles 2,2-diphenyl-1-picrylhydrazine and further products.The reaction between DPPH and N-phenyl-1-naphthylamine is first order with respect to each reactant. The reaction of DPPH with the other amines is retarded by the major product 2,2-diphenyl-1-picrylhydrazine and the kinetics of the over-all reaction are complex. However second-order rate constants and activation energies have been obtained using initial rates of reaction. Possible reaction mechanisms are discussed.

Kinetics of the radical copolymerization of styrene and 2-methoxyethyl methacrylate

1983 ◽  
Vol 48 (9) ◽  
pp. 2656-2665 ◽  
Author(s):  
Jaroslav Stejskal ◽  
Dagmar Straková ◽  
Ondřej Procházka ◽  
Pavel Kratochvíl
Keyword(s):  
Experimental Data ◽  
Molecular Weight ◽  
Kinetic Data ◽  
Radical Copolymerization ◽  
Copolymer Composition ◽  
Monomer Mixture ◽  
Diffusion Controlled ◽  
Kinetics Of ◽  
Best Fit ◽  
Copolymerization Kinetics

Twenty low-conversion statistical copolymers of styrene and 2-methoxyethyl methacrylate with various composition were prepared. The dependence of the copolymer composition, molecular weight, initiation efficiency and other parameters on the composition of the monomer mixture is discussed. Kinetic data are correlated by means of various models of the copolymerization kinetics. The best fit with experimental data is provided by a diffusion-controlled termination model, especially its dyad variant suggested in this study.

Conversion between permeability states of IP3 receptors in cultured smooth muscle cells

1995 ◽  
Vol 269 (3) ◽  
pp. C813-C818 ◽  
Author(s):  
T. Sugiyama ◽  
W. F. Goldman
Keyword(s):  
Rate Constants ◽  
Time Course ◽  
Ip3 Receptors ◽  
A7r5 Cells ◽  
High Conductance State ◽  
Cultured Smooth Muscle Cells ◽  
Induced Changes ◽  
Kinetics Of ◽  
Best Fit ◽  
Conductance State

The kinetics of the effect of inositol 1,4,5-trisphosphate (IP3) on Ca2+ in the sarcoplasmic reticulum (SR) were studied in saponin-permeabilized A7r5 cells. At 0.1 microM, IP3 elicited slow monoexponential declines in SR free Ca2+ concentration ([Ca2+]SR). For IP3 concentration ([IP3]) = 0.2-100 microM, evoked declines in [Ca2+]SR were biphasic and best fit as the sum of two first-order processes with rate constants kfast and kslow. The kfast varied as a function of [IP3] over the range tested, whereas kslow was already maximal when [IP3] = 0.1 microM. To analyze SR Ca2+ release elicited by IP3, the rate constants for IP3-induced changes in the total SR Ca2+ content (kR) were calculated. kR was accurately described only when both [Ca2+]SR and [IP3] were considered together. kR was dependent on IP3 binding to receptors that existed in either of two states, a high-affinity low-conductance state (IP3RH) and a low-affinity high-conductance state (IP3RL). The permeability of IP3RL was 12.28 times larger than that of IP3RH, and the conversion between permeability states as well as changes in both the affinity and cooperativity with which IP3 was bound to IP3RL were mediated by SR Ca2+. This SR Ca(2+)-dependent modulation of the characteristics of IP3 receptors forms the basis for the biphasic time course characteristic of IP3-evoked SR Ca2+ release.

scholarly journals Rhodopsin photoproducts and rod sensitivity in the skate retina.

1977 ◽  
Vol 69 (1) ◽  
pp. 97-120 ◽  
Author(s):  
K P Brin ◽  
H Ripps
Keyword(s):  
Experimental Data ◽  
Computer Simulation ◽  
Rate Constants ◽  
Dark Adaptation ◽  
Photochemical Reactions ◽  
The Other ◽  
Thermal Reactions ◽  
Rate Of Recovery ◽  
Spectral Absorbance ◽  
Kinetics Of

The late photoproducts that result from the isomerization of rhodopsin have been identified in the isolated all-rod retina of the skate by means of rapid spectrophotometry. The sequence in which these intermediates form and decay could be described by a scheme that incorporates two pathways for the degradation of metarhodopsin II (MII) to retinol: one via metarhodopsin III (MIII) and the other (which bypasses MIII) through retinal. Computer simulation of the model yielded rate constants and spectral absorbance coefficients for the late photoproducts which fit experimental data obtained at temperatures ranging from 7 degrees C to 27 degrees C. Comparing the kinetics of the thermal reactions with the changes in rod threshold that occur during dark adaptation indicated that the decay of MII and the fall in receptor thresholds exhibit similarities with regard to their temperature dependence. However, the addition of 2 mM hydroxylamine to a perfusate bathing the retina greatly accelerated the photochemical reactions, but had no significant effect on the rate of recovery of rod sensitivity. It appears, therefore, that the late bleaching intermediates do not control the sensitivities of skate rods during dark adaptation.

Picosecond radical kinetics. Rate constants for ring openings of 2-aryl-substituted cyclopropylcarbinyl radicals

1999 ◽  
Vol 77 (5-6) ◽  
pp. 1123-1135 ◽  
Author(s):  
Martin Newcomb ◽  
Seung-Yong Choi ◽  
Patrick H Toy
Keyword(s):  
Aromatic Ring ◽  
Rate Constants ◽  
The Other ◽  
Radical Reactions ◽  
Methyl Radicals ◽  
Kinetic Methods ◽  
Mechanistic Probe ◽  
Radical Rearrangements ◽  
Kinetics Of

The kinetics of ring openings of a series of eight (trans-2-arylcyclopropyl)methyl radicals (1) were studied by indirect kinetic methods using Barton's PTOC esters as radical precursors and reaction with PhSeH as the competition reaction. The substituents were CF3, F, Me, and OMe located on both the para and meta positions of the aromatic ring. Syntheses of the radical precursors and the products of the radical reactions are described. Kinetics were determined between -43 and 25°C in four cases (CF3 and OMe substituents) and at 0 and 25°C in the other four cases. The rate constants at 25°C ranged from 1.0 × 1011 s-1 (p-CH3) to 4.1 × 1011 s-1 (p-CF3). The relatively large acceleration of the p-CF3 group, ca. 2.5 times as fast as the parent system with Ar = Ph, correlates well with Adam's ΔD substituent parameters but not with other radical substituent parameters. These calibrated radical rearrangements provide a new set of ultrafast reactions that can be applied in mechanistic probe studies.Key words: cyclopropylcarbinyl radical, kinetics, PTOC esters, benzeneselenol.

Kinetics of acid-catalyzed hydration in aqueous solution of 1-methoxy- and 1-methylthio-2-phenylethyne and some related acetylenes

1987 ◽  
Vol 65 (2) ◽  
pp. 441-444 ◽  
Author(s):  
N. Banait ◽  
M. Hojatti ◽  
P. Findlay ◽  
A. J. Kresge
Keyword(s):  
Aqueous Solution ◽  
Proton Transfer ◽  
Isotope Effect ◽  
Rate Constants ◽  
Acid Catalysis ◽  
The Other ◽  
Buffer Solutions ◽  
Hydronium Ion ◽  
Acid Catalyzed ◽  
Kinetics Of

The rates of conversion of C6H5C≡COCH3 to C6H5CH2CO2CH3 were measured in dilute HClO4/H2O, DCIO4/D2O, and H3PO4–H2PO2−/H2O buffer solutions, and the rates of conversion of C6H5C≡CSCH3 to C6H5CH2COSCH3, C6H5C≡CH to C6H5COCH3, 2,4,6-(CH3)3C6H2C≡CH to 2,4,6-(CH3)3C6H2COCH3, and p-CH3OC6H4C≡CCH3 to p-CH3OC6H4COCH2CH3 were measured in concentrated HClO4/H2O solutions, all at 25 °C. The reaction of C6H5C≡COCH3 showed general acid catalysis and gave the isotope effect [Formula: see text], which indicates that it proceeds through rate-determining proton transfer from catalyst to substrate. The hydronium ion catalytic coefficient for this reaction is [Formula: see text], and those for the other four, in the order given above, are [Formula: see text], and 8.5 × 10−6 M−1 s−1. Relative reactivities based on these rate constants are discussed.

The polymerization of styrene by sulphuric acid - II. The kinetics of polymerization in 1:2-dichloroethane

1961 ◽  
Vol 263 (1312) ◽  
pp. 63-74 ◽  
Keyword(s):  
Rate Constants ◽  
Homogeneous Solution ◽  
The Other ◽  
Chain Reaction ◽  
Individual Values ◽  
Kinetics Of Polymerization ◽  
Temperature Range ◽  
Molecular Weights ◽  
Reaction Theory ◽  
Kinetics Of

The polymerization has been studied in homogeneous solution over the temperature range 0 to 35°C. At the upper temperatures the reactions are very fast; over the whole temperature range they are incomplete, giving limited yields of polymer which depend on the initial acid concentration, but not on that of the monomer. The results are described by the non­-stationary chain reaction theory derived in part I. Individual values of all the rate con­stants are obtained at 25°C, and ratios of rate constants at the other temperatures. The molecular weights are relatively low (< 20000) and determined by transfer rather than true termination processes.

scholarly journals Organic exudates promote Fe(II) oxidation in Fe limited cultures of <i>Trichodesmium erythraeum</i>

2017 ◽  
Author(s):  
Hanieh T. Farid ◽  
Kai G. Schulz ◽  
Andrew L. Rose
Keyword(s):  
Rate Constants ◽  
Oxidation Rate ◽  
Growth Cycle ◽  
Batch Cultures ◽  
Trichodesmium Erythraeum ◽  
Luminol Chemiluminescence ◽  
Significant Difference ◽  
Kinetics Of ◽  
Best Fit ◽  
Extracellular Environment

Abstract. A luminol chemiluminescence method was employed to study the oxidation kinetics of Fe(II) in both the absence and the presence of organic exudates released by the marine cyanobacterium Trichodesmium erythraeum. The apparent Fe(II) oxidation rate constant was studied for batch cultures grown with varying Fe' concentrations of 0.05–0.29 and 1.44–2.03 nmol L−1 at pH ranges from 8.1–8.6, corresponding to the change in pH in the cultures during the entire growth cycle. Fe(II) oxidation was accelerated when cells were growing exponentially and gradually decreased towards the stationary phase, consistent with the presence of organic exudates. The best fit of the kinetic model to the data also demonstrated clear differences in apparent Fe(II) oxidation rate constants during different growth phases. However, no significant difference was observed in oxidation rate constants between the two Fe' treatments. These findings suggest that Trichodesmium releases organic compounds into the extracellular environment that influence Fe redox chemistry, potentially affecting Fe bioavailability, and that the nature of the Fe(II) complexes formed is not influenced by Fe limitation of the organism's growth.

Kinetics of esterification of diisopropylphenols with phosphoryl trichloride

1989 ◽  
Vol 54 (8) ◽  
pp. 2099-2104
Author(s):  
Miroslav Magura ◽  
Ján Vojtko ◽  
Ján Ilavský
Keyword(s):  
Liquid Phase ◽  
Differential Equations ◽  
Rate Constants ◽  
Activation Energies ◽  
The Other ◽  
Kinetics Of

The title liquid-phase isothermal esterification kinetics have been measured in the temperature intervals of 110-125 and 110-160 °C for 2,4- and 2,6-diisopropylphenols, resp. The values measured have been used to calculate the rate constants of the respective three steps and to determine the activation energies. 2,6-Diisopropylphenol has been found to react only to the first degree, and the rate constants of the other two reaction steps (k2, k3) were only calculated from the differential equations given by means of a computer.

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