Determination of Best-Fit Rate Constants in Chemical Kinetics

1966 ◽  
Vol 5 (2) ◽  
pp. 181-184 ◽  
Author(s):  
W. E. Ball ◽  
L. C. D. Groenweghe
Keyword(s):  
Chemical Kinetics ◽  
Rate Constants ◽  
Best Fit

Determination of rate constants of redox reactions of second order from current-less potential-time curves by a simplified graphical-numerical method

1983 ◽  
Vol 48 (5) ◽  
pp. 1358-1367 ◽  
Author(s):  
Antonín Tockstein ◽  
František Skopal
Keyword(s):  
Numerical Method ◽  
Explicit Form ◽  
Rate Constant ◽  
Optimization Algorithm ◽  
Rate Constants ◽  
Redox Reactions ◽  
Second Order ◽  
Wide Region ◽  
Recurrent Formula

A method for constructing curves is proposed that are linear in a wide region and from whose slopes it is possible to determine the rate constant, if a parameter, θ, is calculated numerically from a rapidly converging recurrent formula or from its explicit form. The values of rate constants and parameter θ thus simply found are compared with those found by an optimization algorithm on a computer; the deviations do not exceed ±10%.

Determination of the Accurate Values of the Rate Constant and Thermodynamic Parameters for the Rotation About the C(sp2)-C(aryl) Bond; Adamantan-1-yl 3-Bromo-2,4,6-trimethylphenyl Ketone

1998 ◽  
Vol 63 (7) ◽  
pp. 955-966
Author(s):  
Eva Přibylová ◽  
Miroslav Holík
Keyword(s):  
Thermodynamic Parameters ◽  
Shape Analysis ◽  
Rate Constants ◽  
Line Shape ◽  
Microsoft Excel ◽  
Hindered Rotation ◽  
H Nmr ◽  
Line Shape Analysis ◽  
Coalescence Temperature

Four programs for the 1H NMR line shape analysis: two commercial - Winkubo (Bruker) and DNMR5 (QCPE 165) and two written in our laboratory - Newton (in Microsoft Excel) and Simtex (in Matlab) have been tested in order to get highly accurate rate constants of the hindered rotation about a single bond. For this purpose four testing criteria were used, two of them were also developed by us. As supplementary determinations the rate constants obtained for the coalescence temperature and for the thermal racemization of chromatographically separated enantiomers were used which fitted well the temperature dependence of the rate constants determined by the line shape analysis. As a test compound adamantan-1-yl 3-bromo-2,4,6-trimethylphenyl ketone was prepared and studied. It was shown that supermodified simplex method used in our algorithm (Simtex), though time consuming, gives the most accurate values of the rate constants and consequently the calculated thermodynamic parameters Ea, ∆H≠, and ∆S≠ lay in relatively narrow confidence intervals.

Determination of the Nucleophilicity of Tricarbonyliron Coordinated Cyclohepta-1,3,5-triene

1999 ◽  
Vol 64 (11) ◽  
pp. 1770-1779 ◽  
Author(s):  
Herbert Mayr ◽  
Karl-Heinz Müller
Keyword(s):  
Gibbs Energy ◽  
Ambient Temperature ◽  
Rate Constants ◽  
Second Order ◽  
Order Rate ◽  
Electrophilic Additions ◽  
Kinetics Of

The kinetics of the electrophilic additions of four diarylcarbenium ions (4a-4d) to tricarbonyl(η4-cyclohepta-1,3,5-triene)iron (1) have been studied photometrically. The second-order rate constants match the linear Gibbs energy relationship log k20 °C = s(E + N) and yield the nucleophilicity parameter N(1) = 3.69. It is concluded that electrophiles with E ≥ -9 will react with complex 1 at ambient temperature.

Interfacial catalysis by phospholipase A2: determination of the interfacial kinetic rate constants

Biochemistry ◽  
1991 ◽  
Vol 30 (29) ◽  
pp. 7283-7297 ◽  
Author(s):  
Otto G. Berg ◽  
Bao Zhu Yu ◽  
Joe Rogers ◽  
Mahendra Kumar Jain
Keyword(s):  
Phospholipase A2 ◽  
Rate Constants ◽  
Kinetic Rate ◽  
Kinetic Rate Constants ◽  
Interfacial Catalysis

scholarly journals Reactor rate modulation oscillation analysis with two detectors in Double Chooz

2021 ◽  
Vol 2021 (1) ◽  
Author(s):  
T. Abrahão ◽  
◽  
H. Almazan ◽  
J. C. dos Anjos ◽  
S. Appel ◽  
...  
Keyword(s):  
Reactor Power ◽  
Background Model ◽  
Fast Neutrons ◽  
Mixing Angle ◽  
Oscillation Analysis ◽  
Central Value ◽  
Double Chooz ◽  
Model Independent ◽  
Best Fit

Abstract A θ13 oscillation analysis based on the observed antineutrino rates at the Double Chooz far and near detectors for different reactor power conditions is presented. This approach provides a so far unique simultaneous determination of θ13 and the total background rates without relying on any assumptions on the specific background contributions. The analysis comprises 865 days of data collected in both detectors with at least one reactor in operation. The oscillation results are enhanced by the use of 24.06 days (12.74 days) of reactor-off data in the far (near) detector. The analysis considers the $$ {\overline{\nu}}_e $$ ν ¯ e interactions up to a visible energy of 8.5 MeV, using the events at higher energies to build a cosmogenic background model considering fast-neutrons interactions and 9Li decays. The background-model-independent determination of the mixing angle yields sin2(2θ13) = 0.094 ± 0.017, being the best-fit total background rates fully consistent with the cosmogenic background model. A second oscillation analysis is also performed constraining the total background rates to the cosmogenic background estimates. While the central value is not significantly modified due to the consistency between the reactor-off data and the background estimates, the addition of the background model reduces the uncertainty on θ13 to 0.015. Along with the oscillation results, the normalization of the anti-neutrino rate is measured with a precision of 0.86%, reducing the 1.43% uncertainty associated to the expectation.

Sign in / Sign up

Export Citation Format

Share Document