Temperature dependence of the preexponential factors for the rate constants of bimolecular and unimolecular gas reactions

1973 ◽  
Vol 6 (3) ◽  
pp. 330-334 ◽  
Author(s):  
M. P. Mulyava ◽  
V. U. Shevchuk
1981 ◽  
Vol 46 (12) ◽  
pp. 3104-3109 ◽  
Author(s):  
Miroslav Ludwig ◽  
Oldřich Pytela ◽  
Miroslav Večeřa

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.


1995 ◽  
Vol 73 (12) ◽  
pp. 2137-2142 ◽  
Author(s):  
A.J. Elliot ◽  
M.P. Chenier ◽  
D.C. Ouellette

In this publication we report: (i) the rate constants for reaction of the hydrated electron with 1-hexyn-3-ol ((8.6 ± 0.3) × 108 dm3 mol−1 s−1 at 18 °C), cinnamonitrile ((2.3 ± 0.2) × 1010 dm3 mol−1 s−1 at 20 °C), and 1,3-diethyl-2-thiourea ((3.5 ± 0.3) × 108 dm3 mol−1 s−1 at 22 °C). For cinnamonitrile and diethylthiourea, the temperature dependence up to 200 °C and 150 °C, respectively, is also reported; (ii) the rate constants for the reaction of the hydroxyl radical with 1-hexyn-3-ol ((5.5 ± 0.5) × 109 dm3 mol−1 s−1 at 20 °C), cinnamonitrile ((9.2 ± 0.3) × 109 dm3 mol−1 s−1 at 21 °C), and diethylthiourea ((8.0 ± 0.8) × 108 dm3 mol−1 s−1 at 22 °C). For cinnamonitrile, the temperature dependence up to 200 °C is also reported; (iii) the rate constant for the hydrogen atom reacting with 1-hexyn-3-ol ((4.3 ± 0.4) × 109 dm3 mol−1 s−1 at 20 °C). Keywords: radiolysis, corrosion inhibitors, rate constants.


1981 ◽  
Vol 27 (5) ◽  
pp. 753-755 ◽  
Author(s):  
P A Adams ◽  
M C Berman

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).


1971 ◽  
Vol 26 (10) ◽  
pp. 1010-1016 ◽  
Author(s):  
Renate Voigt ◽  
Helmut Wenck ◽  
Friedhelm Schneider

First order rate constants of the reaction of a series of SH-, imidazole- and imidazole/SH-compounds with FDNB as well as their pH- and temperature dependence were determined. Some of the tested imidazole/SH-compounds exhibit a higher nucleophilic reactivity as is expected on the basis of their pKSH-values. This enhanced reactivity is caused by an activation of the SH-groups by a neighbouring imidazole residue. The pH-independent rate constants were calculated using the Lindley equation.The kinetics of DNP-transfer from DNP-imidazole to SH-compounds were investigated. The pH-dependence of the reaction displays a maximum curve. Donor in this reaction is the DNP-imidazolecation and acceptor the thiolate anion.The reaction rate of FDNB with imidazole derivatives is two to three orders of magnitude slower than with SH-compounds.No inter- or intra-molecular transfer of the DNP-residue from sulfure to imidazole takes place.


2001 ◽  
Vol 65 (6) ◽  
pp. 701-707 ◽  
Author(s):  
Y. Morizet ◽  
S. C. Kohn ◽  
R. A. Brooker

AbstractThe thermodynamics and kinetics of CO2 speciation in silicate melts have been studied by measuring the concentration of CO2mol and carbonate in jadeite glass annealed at 575, 450 and 400°C. Assuming that the reaction is1where CO2mol..Obr represents a CO2 molecule weakly bonded to a bridging oxygen in the network and CO3 represents a bridging carbonate group with no net negative charge, ΔH for the reaction is –17 (+4/–8) kJ mol−1 and ΔS is –24 (+6/–9) J K−1 mol−1. The rate of equilibration of the species was measured at each temperature and the rate constants were deduced. The temperature dependence of the rate constants was used to determine the activation energy of the forward and reverse reactions which are 68 (+3/–31) kJ mol−1 and 86 (+1/–69) kJ mol−1 respectively. The data suggest that CO2mol may be much more abundant in silicate melts than previously assumed on the basis of studies of CO2-bearing glasses. Models of solubility, diffusion, and isotope fractionation should take this into account.


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