Effect of pressure on the rates of hydrolysis of allyl chlorides

1969 ◽  
Vol 47 (8) ◽  
pp. 1369-1373 ◽  
Author(s):  
A. B. Lateef ◽  
J. B. Hyne
Keyword(s):  
Temperature Dependence ◽  
Pressure Dependence ◽  
Activation Volume ◽  
Allyl Chloride ◽  
Activation Parameters ◽  
The Other ◽  
Effect Of Pressure ◽  
Hydrolysis Of

The pressure dependence of the rates of hydrolysis of allyl chloride and α-, β-, and γ-methyl allyl chlorides has been examined. The significance of the activation volumes, ΔV*, and their pressure dependence, dΔV*/dP, is discussed. These activation parameters indicate an SN2 mechanism for allyl and β-methyl allyl chloride and an SN1 or intermediate character mechanism for the other methyl substituted allyl chlorides investigated. The results are compared with the corresponding ΔH* and ΔCP* measurements of Robertson and co-workers. The temperature dependence of the activation volume, dΔV*/dT, for the solvolysis of the parent allyl chloride has been measured and found to be small and negative.

ON THE PRESSURE DEPENDENCE OF REACTION RATES

1966 ◽  
Vol 44 (18) ◽  
pp. 2193-2203 ◽  
Author(s):  
H. S. Golinkin ◽  
W. G. Laidlaw ◽  
J. B. Hyne
Keyword(s):  
Pressure Dependence ◽  
Benzyl Chloride ◽  
Activation Volume ◽  
Functional Dependence ◽  
Quadratic Function ◽  
Activation Parameters ◽  
Reaction Rates ◽  
General Applicability ◽  
Order Polynomial ◽  
Derivatives Of

The functional dependence of the rate constant for benzyl chloride solvolysis on pressure is investigated with a view to obtaining reliable values of the activation parameters. It is concluded that a second order polynomial is the best description of this system, reproducing the experimental data with a greater degree of precision than the other published functions. A method for determining the precision of the derivatives of the logarithmic rate is presented, and the pressure dependence of the activation volume is demonstrated. Various systems from the literature are analyzed to demonstrate the general applicability of the quadratic function.

Kinetics and mechanism of the base hydrolysis of some trans-dihalogeno(cyclam)rhodium(III) complexes

1978 ◽  
Vol 56 (5) ◽  
pp. 709-713 ◽  
Author(s):  
H. L. Chung ◽  
E. J. Bounsall
Keyword(s):  
Rate Constants ◽  
Activation Parameters ◽  
The Other ◽  
Base Hydrolysis ◽  
Trans Effect ◽  
First Order ◽  
Class B ◽  
Pseudo First Order ◽  
Hydrolysis Of ◽  
Kinetic Class

The base hydrolysis of trans-[Rh(cyclam)XY]+ (cyclam = 1,4,8,11-tetraazacyclotetradecane; X− and Y− = Cl−, Br−, and I−) are studied in aqueous solution over a range of OH− concentration and at various temperatures. The kinetics are done at a constant ionic strength with excess of [OH−] (smallest ratio = 200:1) so that pseudo first order rate constants are obtained for all the determinations. All of the reactions proceed with complete retention of configuration, and no trans-to-cis isomerization is found. The kinetic trans effect of these complexes is I− > Br− > Cl− on a rate basis, but based on ΔH≠, I− > Br− = Cl−. These Rh(III) complexes exhibit kinetic class (b) character on the ΔH≠ basis. The results of the rate constants and the activation parameters are interpreted in ternis of an SN1CB mechanism. The behavior of these complexes is compared to that of the other analogous complexes.

A FACILE SYNTHESIS AND REACTIONS OF AMINO SELENOLO[2,3-b]PYRIDINE CARBOXYLATE

2015 ◽  
Vol 12 (1) ◽  
pp. 3910-3918 ◽  
Author(s):  
Dr Remon M Zaki ◽  
Prof Adel M. Kamal El-Dean ◽  
Dr Nermin A Marzouk ◽  
Prof Jehan A Micky ◽  
Mrs Rasha H Ahmed
Keyword(s):  
Biological Activity ◽  
Carbonyl Compounds ◽  
Mass Spectra ◽  
The Other ◽  
Pyridine Derivatives ◽  
Facile Synthesis ◽  
High Biological Activity ◽  
Basic Hydrolysis ◽  
Pyridine Carboxylate ◽  
Hydrolysis Of

 Incorporating selenium metal bonded to the pyridine nucleus was achieved by the reaction of selenium metal with 2-chloropyridine carbonitrile 1 in the presence of sodium borohydride as reducing agent. The resulting non isolated selanyl sodium salt was subjected to react with various α-halogenated carbonyl compounds to afford the selenyl pyridine derivatives 3a-f  which compounds 3a-d underwent Thorpe-Ziegler cyclization to give 1-amino-2-substitutedselenolo[2,3-b]pyridine compounds 4a-d, while the other compounds 3e,f failed to be cyclized. Basic hydrolysis of amino selenolo[2,3-b]pyridine carboxylate 4a followed by decarboxylation furnished the corresponding amino selenolopyridine compound 6 which was used as a versatile precursor for synthesis of other heterocyclic compound 7-16. All the newly synthesized compounds were established by elemental and spectral analysis (IR, 1H NMR) in addition to mass spectra for some of them hoping these compounds afforded high biological activity.

Salt effect in hydrolysis of 3-acyl-1,3-diphenyltriazenes

1981 ◽  
Vol 46 (12) ◽  
pp. 3104-3109 ◽  
Author(s):  
Miroslav Ludwig ◽  
Oldřich Pytela ◽  
Miroslav Večeřa
Keyword(s):  
Sodium Chloride ◽  
Temperature Dependence ◽  
Potassium Chloride ◽  
Rate Constants ◽  
Zinc Sulphate ◽  
Salt Effect ◽  
Sodium Sulphate ◽  
Potassium Sulphate ◽  
Lithium Sulphate ◽  
Hydrolysis Of

Rate constants of non-catalyzed hydrolysis of 3-acetyl-1,3-diphenyltriazene (I) and 3-(N-methylcarbamoyl)-1,3-diphenyltriazene (II) have been measured in the presence of salts (ammonium chloride, potassium chloride, lithium chloride, sodium chloride and bromide, ammonium sulphate, potassium sulphate, lithium sulphate, sodium sulphate and zinc sulphate) within broad concentration ranges. Temperature dependence of the hydrolysis of the substrates studied has been measured in the presence of lithium sulphate within temperature range 20° to 55 °C. The results obtained have been interpreted by mechanisms of hydrolysis of the studied substances.

A kinetic standard for precise calibration of spectrophotometer cell temperature.

1981 ◽  
Vol 27 (5) ◽  
pp. 753-755 ◽  
Author(s):  
P A Adams ◽  
M C Berman
Keyword(s):  
Temperature Dependence ◽  
Rate Constants ◽  
Cell Temperature ◽  
First Order ◽  
Order Rate ◽  
Acid Catalyzed ◽  
Pseudo First Order ◽  
Hydrolysis Of

Abstract We describe a simple, highly reproducible kinetic technique for precisely measuring temperature in spectrophotometric systems having reaction cells that are inaccessible to conventional temperature probes. The method is based on the temperature dependence of pseudo-first-order rate constants for the acid-catalyzed hydrolysis of N-o-tolyl-D-glucosylamine. Temperatures of reaction cuvette contents are measured with a precision of +/- 0.05 degrees C (1 SD).

Neutral Solvolysis of Acyl Carbon and the Temperature Dependence of the Kinetic Solvent Isotope Effect

1975 ◽  
Vol 53 (6) ◽  
pp. 869-877 ◽  
Author(s):  
B. Rossall ◽  
R. E. Robertson
Keyword(s):  
Temperature Dependence ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Acyl Carbon ◽  
Rate Of Hydrolysis ◽  
Solvent Isotope ◽  
Neutral Conditions ◽  
Hydrolysis Of

The temperature dependence of the rate of hydrolysis of benzoic, phthalic, and succinic anhydrides have been determined in H2O and D2O under "neutral" conditions. Corresponding data have been obtained for methyl trifluoroacetate. While both series supposedly react by the same BAc2 mechanism, remarkable differences are made obvious by this investigation. Possible sources of such differences are proposed.

Temperature Dependence of the Intervalley Deformation Potential of GaAs/AlAs Superlattices Under Hydrostatic Pressure

1997 ◽  
Vol 499 ◽  
Author(s):  
S. Guha ◽  
Q. Cai ◽  
M. Chandrasekhar ◽  
H. R. Chandrasekhar ◽  
Hyunjung Kim ◽  
...  
Keyword(s):  
Hydrostatic Pressure ◽  
Temperature Dependence ◽  
Pressure Dependence ◽  
Type I ◽  
Type Ii ◽  
Deformation Potential ◽  
Intervalley Scattering

ABSTRACTWe have studied the pressure dependence of the type-I and type-II transitions in (GaAs)m/(AlAs)m superlattices by photoluminescence (PL) spectroscopy. From the study of PL linewidths of the type-I exciton as a function of pressure and temperature, we determine the intervalley deformation potential. Beyond the type-I and type-II crossover, the PL linewidth increases both as a function of pressure and temperature. We find that the electron-phonon deformation potential for Γ-X intervalley scattering varies with temperature.

THE ALDOBIOURONIC ACIDS OF HEMICELLULOSE B OF OAT HULLS

1956 ◽  
Vol 34 (3) ◽  
pp. 338-344 ◽  
Author(s):  
E. L. Falconer ◽  
G. A. Adams
Keyword(s):  
Glucuronic Acid ◽  
The Other ◽  
Partial Hydrolysis ◽  
Oat Hulls ◽  
Hydrolysis Of

Partial hydrolysis of hemicellulose B from oat hulls yielded two aldobiouronic acids, which were identified as 2-O-(4-O-methyl-α-D-glucopyruronosyl)-D-xylose and 2-O-(α-D-glucopyruronosyl)-D-xylose respectively. In addition, two aldotriouronic acids were isolated, one yielding on hydrolysis xylose and 4-O-methyl-glucuronic acid, and the other, xylose, galactose, and glucurone.

Effect of pressure on the α-amylase catalyzed hydrolysis of starch

1964 ◽  
Vol 6 (4) ◽  
pp. 469-471 ◽  
Author(s):  
Richard G. Griskey ◽  
Thomas Richter
Keyword(s):  
Effect Of Pressure ◽  
Hydrolysis Of

Heat capacity of activation for the hydrolysis of methanesulfonyl chloride and benzenesulfonyl chloride in light and heavy water

1969 ◽  
Vol 47 (22) ◽  
pp. 4199-4206 ◽  
Author(s):  
R. E. Robertson ◽  
B. Rossall ◽  
S. E. Sugamori ◽  
L. Treindl
Keyword(s):  
Heat Capacity ◽  
Free Energy ◽  
Temperature Dependence ◽  
Heavy Water ◽  
Bond Formation ◽  
Sulfonyl Chlorides ◽  
Benzenesulfonyl Chloride ◽  
Methanesulfonyl Chloride ◽  
Hydrolysis Of ◽  
Parameter Temperature Dependence

Rates of solvolysis of methanesulfonyl chloride and benzenesulfonyl chloride have been determined in H2O and D2O. The free energy, enthalpy, entropy, and heat capacity of activation were calculated. The exceptional accuracy of the data permitted an estimation of dΔCp≠/dT from a four parameter temperature dependence of the kinetic rates.From these data we conclude that both sulfonyl chlorides hydrolyse by the same mechanism (Sn2) The change in R from CH3 to C6H5 in RSO2Cl did not alter ΔCp≠ but ΔS≠ (20°) was changed from −8.32 to −13.25 cal deg−1 mole−1, respectively. The significance of this difference is attributed to the probability of bond formation rather than to differences in solvent reorganization.

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