Non-linear arrhenius behaviour of the rate constants of some activation-controlled reactions of the hydrated electron in the temperature range 20–200 °C

1992 ◽  
Vol 88 (19) ◽  
pp. 2833-2836 ◽  
Author(s):  
George V. Buxton ◽  
Stuart R. Mackenzie
Keyword(s):  
Rate Constants ◽  
Hydrated Electron ◽  
Temperature Range ◽  
Non Linear

Radiolysis studies on the corrosion inhibitors 1 -hexyn-3-ol, cinnamonitrile, and 1,3-diethyl-2-thiourea

1995 ◽  
Vol 73 (12) ◽  
pp. 2137-2142 ◽  
Author(s):  
A.J. Elliot ◽  
M.P. Chenier ◽  
D.C. Ouellette
Keyword(s):  
Hydrogen Atom ◽  
Hydroxyl Radical ◽  
Temperature Dependence ◽  
Rate Constant ◽  
Rate Constants ◽  
Corrosion Inhibitors ◽  
Hydrated Electron

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.

Non-linear ultrasonic and viscoelastic properties of gelatine investigated in the temperature range of 30 °C–60 °C

2021 ◽  
Vol 33 (2) ◽  
pp. 022002
Author(s):  
Jan Dirk Heyns ◽  
Esam T. Ahmed Mohamed ◽  
Nico F. Declercq
Keyword(s):  
Viscoelastic Properties ◽  
Temperature Range ◽  
Non Linear

MECHANISM AND KINETICS OF THE CH3CH2C(O)OCH2CH3 + OH REACTION: A THEORETICAL STUDY

2011 ◽  
Vol 10 (05) ◽  
pp. 691-709 ◽  
Author(s):  
CONG HOU ◽  
CHENG-GANG CI ◽  
TONG-YIN JIN ◽  
YONG-XIA WANG ◽  
JING-YAO LIUM
Keyword(s):  
Rate Constants ◽  
Hydrogen Abstraction ◽  
Negative Temperature ◽  
State Theory ◽  
Measured Temperature ◽  
Temperature Range ◽  
Global Rate ◽  
Abstraction Reaction ◽  
Lower Temperature ◽  
Kinetic Calculations

The hydrogen abstraction reaction of CH 3 CH 2 C(O)OCH 2 CH 3 + OH has been studied theoretically by dual-level direct dynamics method. Six H-abstraction channels were found for this reaction. The required potential energy surface information for the kinetic calculations was obtained at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. The rate constants were calculated by the improved canonical variational transition-state theory with small-curvature tunneling correction (ICVT/SCT) approach in the temperature range of 200–2000 K. It is shown that the "methylene H-abstraction" from the alkoxy end of the ester CH 3 CH 2 C(O)OCH 2 CH 3 is the dominant channel at lower temperature (< 400 K), while the other channels from the acetyl end should be taken into account as the temperature increases and become the competitive ones at higher temperature. The calculated global rate constants are in good agreement with the experimental ones in the measured temperature range and exhibit a negative temperature dependence below 500 K. A four-parameter rate constant expression was fitted from the calculated kinetic data between 200–2000 K.

scholarly journals STUDY OF CARBON DIOXIDE ADSORPTION ON CHROMIUM OXIDE AND GALLIUM OXIDE CATALYSTS ON BASIS OF NON-LINEAR RELAXATION TIMES

2018 ◽  
Vol 61 (2) ◽  
pp. 46 ◽  
Author(s):  
Nikolay I. Kol'tsov
Keyword(s):  
Carbon Dioxide ◽  
Relaxation Time ◽  
Chromium Oxide ◽  
Rate Constants ◽  
Gallium Oxide ◽  
Relaxation Times ◽  
Oxide Catalysts ◽  
Linear Relaxation ◽  
Adsorption And Desorption ◽  
Non Linear

Recently the analysis of transient regimes of chemical reactions is paid much attention. This is due to the fact that the time-dependent relaxation modes prior to achieving steady states contain important information about the features of the reactions. During unsteady mode the changes in reactant concentrations and rate of the reaction in time are observed. These changes are due to their own relaxation processes, depending on the structure of the reaction mechanism. A complete study of the reaction mechanism involves the study of the relaxation characteristics both near and away from the stationary state. Linear relaxation time describes the local transient modes near the steady state and it is calculated as the time decrease deviations of reactant concentrations from steady-state values in the e-times. Non-linear relaxation time describes the overall behavior reactions and it can be evaluated through the reaction time from the initial state to a stationary. Depending on the structural features of reactions ratio to determine the non-linear relaxation time through of reactions parameters (rate constants stages and reactant concentrations) differ significantly. The establishment of such ratio for a particular reaction allows getting more information to identify the mechanism and the constituent rate constants of its stages. The mechanism of any catalytic reaction involves stages adsorption of one or more of the starting materials on the catalyst surface. As a rule these stages are initial remaining stages of chemical transformation of reactants adsorbed forms follow them. Therefore, it is necessary to have the data on these stages and rate constants of adsorption of reagents on the catalyst surface. Earlier by author the method for estimating the values of the rate constants of adsorption and desorption by linear relaxation times was described. This method was used for determine of mechanism and kinetic parameters of process of adsorption of carbon dioxide on the chromium oxide and gallium oxide catalysts. In this article the method for estimating the values of the rate constants of adsorption and desorption by non-linear relaxation times for this process is described. The previously found CO2 dissociative adsorption mechanism was proved by the obtained results. The intervals of values changes of the rate constants of adsorption and desorption of carbon dioxide on the gallium oxide and chromium oxide catalysts were defined.Forcitation:Kol’tsov N.I. Study of carbon dioxide adsorption on chromium oxide and gallium oxide catalysts on basis of non-linear relaxation times. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 2. P. 46-52

Reactions of trifluoromethyl radicals. V. Hydrogen abstraction from methyl acetate and methyl (2H3)Acetate

1980 ◽  
Vol 33 (7) ◽  
pp. 1437
Author(s):  
NL Arthur ◽  
PJ Newitt
Keyword(s):  
Isotope Effect ◽  
Rate Constants ◽  
Methoxy Group ◽  
Methyl Acetate ◽  
Kinetic Isotope Effect ◽  
Hydrogen Abstraction ◽  
Activation Energies ◽  
Temperature Range ◽  
Kinetic Isotope ◽  
Acetyl Group

Hydrogen abstraction by CF3 radicals from CH3COOCH3 and CD3COOCH3 has been studied in the temperature range 78-242°, and data have been obtained for the reactions: CF3 + CH3COOCH3 → CF3H+[C3H5O2] �������������(3) CF3 + CH3COOCH3 → CF3H+CH2COOCH3������������ (4) CF3 + CD3COOCH3 → CF3D+CD2COOCH3������������ (6) CF3 + CD3COOCH3 → CF3H+CD3COOCH2������������ (7) The corresponding rate constants, based on the value of 1013.36 cm3 mol-1 S-1 for the recombination of CF3 radicals, are given by (k in cm3 mol-1 s-1 and E in J mol-1): logk3 = (11.52�0.05)-(35430�380)/19.145T ���� (3)logk4 = (11.19�0.07)-(34680�550)/19.145T ���� (4)logk6 = (11.34�0.06)-(46490�490)/19.145T ���� (6)logk7 = (11.26�0.05)-(36440�400)/19.145T ���� (7)At 400 K, 59% of abstraction occurs from the acetyl group, and 41 % from the methoxy group. The kinetic isotope effect at 400 K for attack on the acetyl group is 25, due mainly to a difference in activation energies.

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