Accurate Calculation of the Energy Barriers and Rate Constants of the Large-size Molecular Reaction System for Abstraction from Alkyl Hydroperoxides

2018 ◽  
Vol 76 (4) ◽  
pp. 311 ◽  
Author(s):  
Fangfang Chen ◽  
Xiaohui Sun ◽  
Qian Yao ◽  
Zerong Li ◽  
Jingbo Wang ◽  
...  
Keyword(s):  
Rate Constants ◽  
Reaction System ◽  
Accurate Calculation ◽  
Energy Barriers ◽  
Large Size ◽  
Alkyl Hydroperoxides ◽  
Molecular Reaction

scholarly journals Accurate Calculation of the Energy Barriers and Rate Constants of Hydrogen Abstraction from Alkanes by Hydroperoxyl Radical

2017 ◽  
Vol 33 (4) ◽  
pp. 763-768 ◽  
Author(s):  
Qian YAO ◽  
◽  
Li-Juan PENG ◽  
Ze-Rong LI ◽  
Xiang-Yuan LI ◽  
...  
Keyword(s):  
Rate Constants ◽  
Hydrogen Abstraction ◽  
Accurate Calculation ◽  
Energy Barriers ◽  
Hydroperoxyl Radical

Reaction kinetics of OH radicals with glutaric acid and adipic acid in the aqueous phase

2021 ◽  
Author(s):  
Liang Wen ◽  
Thomas Schaefer ◽  
Hartmut Herrmann
Keyword(s):  
Aqueous Phase ◽  
Adipic Acid ◽  
Rate Constants ◽  
Density Functional ◽  
Glutaric Acid ◽  
Radical Reaction ◽  
Basis Set ◽  
Oh Radicals ◽  
Oh Radical ◽  
Energy Barriers

<p>Dicarboxylic acids (DCAs) are widely distributed in atmospheric aerosols and cloud droplets and are mainly formed by the oxidation of volatile organic compounds (VOCs). For example, glutaric acid and adipic acid are two kinds of the DCAs that can be oxidized by hydroxyl radical (‧OH) reactions in the aqueous phase of aerosols and droplets. In the present study, the temperature- and pH-dependent rate constants of the aqueous OH radical reactions of the two DCAs were investigated by a laser flash photolysis-long path absorption setup using the competition kinetics method. Based on speciation calculations, the OH radical reaction rate constants of the fully protonated (H<sub>2</sub>A), deprotonated (HA<sup>-</sup>) and fully deprotonated (A<sup>2-</sup>) forms of the two DCAs were determined. The following Arrhenius expressions for the T-dependency of the OH radical reaction of glutaric acid, k(T, H<sub>2</sub>A) = (3.9 ± 0.1) × 10<sup>10</sup> × exp[(-1270 ± 200 K)/T], k(T, HA<sup>-</sup>) = (2.3 ± 0.1) × 10<sup>11</sup> × exp[(-1660 ± 190 K)/T], k(T, A<sup>2-</sup>) = (1.4 ± 0.1) × 10<sup>11</sup> × exp[(-1400 ± 170 K)/T] and adipic acid, k(T, H<sub>2</sub>A) = (7.5 ± 0.2) × 10<sup>10</sup> × exp[(-1210 ± 170 K)/T], k(T, HA<sup>-</sup>) = (9.5 ± 0.3) × 10<sup>10</sup> × exp[(-1200 ± 200 K)/T], k(T, A<sup>2-</sup>) = (8.7 ± 0.2) × 10<sup>10</sup> × exp[(-1100 ± 170 K)/T] (in unit of L mol<sup>-1</sup> s<sup>-1</sup>) were derived.</p><p>The energy barriers of the H-atom abstractions were simulated by the Density Functional Theory calculations run with the GAUSSIAN package using the M06-2X method and the basis set m062x/6-311++g(3df,2p). The results showed that the energy barriers were lower at the C<sub>β</sub>-atoms and are higher at the C<sub>α</sub>-atoms of the two DCAs, clearly suggesting that the H-atom abstractions occurred predominately at the C<sub>β</sub>-atoms. In addition, the ionizations can enhance the electrostatic effects of the carboxyl groups, significantly reducing the energy barriers, leading to the order of OH radical reactivity as  <  < . This study intends to better characterize the losing processes of glutaric acid and adipic acid in atmospheres.</p>

Carbohydrates in alkaline systems. II. Kinetics of the transformation and degradation reactions of cellobiose, cellobiulose, and 4-O-β-D-glucopyranosyl-D-mannose in 1 M sodium hydroxide at 22 °C

1969 ◽  
Vol 47 (21) ◽  
pp. 3957-3964 ◽  
Author(s):  
Donald J. MacLaurin ◽  
John W. Green
Keyword(s):  
Sulfuric Acid ◽  
Sodium Hydroxide ◽  
Column Chromatography ◽  
Rate Constants ◽  
Reaction Rate ◽  
Reaction System ◽  
Reaction Rate Constants ◽  
Degradation Reactions ◽  
Fructose 2 ◽  
Kinetics Of

Rates of isomerization, epimerization, and degradation reactions were measured for cellobiose (7), cellobiulose (8), and 4-O-β-D-glucopyranosyl-D-mannose (9) at 0.001 M in 1 M NaOH under N2 in the dark at 22 °C. Reaction system resolution was by column chromatography on anion resins in the borate form. Assay for D-glucose (1), D-fructose (2), D-mannose (3), and 7,8, and 9 was by continuous automated colorimetry of column effluent with orcinol–sulfuric acid as reagent. Reaction rate constants (h−1) found: k78 0.078, k79 0.0005, k7,10 0.002, k87 0.022, k89 0.003 k81 0.065, k8,12 0.023, k97 0.002, k98 0.013, k9,11 0.006 where 10,11, and 12 are other products than 1,2,3,7,8, and 9. Details for preparation of 8 and 9 are given.

Carbohydrates in alkaline systems. I. Kinetics of the transformation and degradation of D-glucose, D-fructose, and D-mannose in 1 M sodium hydroxide at 22 °C

1969 ◽  
Vol 47 (21) ◽  
pp. 3947-3955 ◽  
Author(s):  
Donald J. MacLaurin ◽  
John W. Green
Keyword(s):  
Sulfuric Acid ◽  
Sodium Hydroxide ◽  
Column Chromatography ◽  
Rate Constants ◽  
Reaction Rate ◽  
Reaction System ◽  
Reaction Rate Constants ◽  
Degradation Reactions ◽  
Fructose 2 ◽  
Kinetics Of

Rates of isomerization, epimerization, and degradation reactions were measured for D-glucose (1), D-fructose (2), and D-mannose (3) at 0.002 M in 1 M NaOH under N2 in the dark at 22 °C. Reaction system resolution was by column chromatography on anion resins in the borate form. Assay for 1, 2, and 3 was by continuous automated colorimetry of column effluent using orcinol/sulfuric acid as a reagent. D-Allose and D-altrose were not detected. Reaction rate constants (h−1) found: k12 0.038, k13 0.0005, k15 0.002, k21 0.036, k23 0.006, k24 0.072, k31 0.0005, k32 0.011, k36 0.002, where 4, 5, and 6 are products formed from 1, 2, or 3, respectively.

scholarly journals Equilibrium of Phosphointermediates of Sodium and Potassium Ion Transport Adenosine Triphosphatase

1997 ◽  
Vol 109 (5) ◽  
pp. 537-554 ◽  
Author(s):  
Kuniaki Suzuki ◽  
Robert L. Post
Keyword(s):  
Ion Transport ◽  
Rate Constants ◽  
Adenosine Triphosphatase ◽  
Reaction System ◽  
Potassium Ion ◽  
Hydrolysis Rate ◽  
Decay Kinetics ◽  
Potassium Ion Transport ◽  
Pool Model ◽  
Sodium And Potassium

Sodium and potassium ion transport adenosine triphosphatase accepts and donates a phosphate group in the course of its reaction sequence. The phosphorylated enzyme has two principal reactive states, E1P and E2P. E1P is formed reversibly from ATP in the presence of Na+ and is precursor to E2P, which equilibrates with Pi in the presence of K+. We studied equilibrium between these states at 4°C and the effect of Na+ on it. To optimize the reaction system we used a Hofmeister effect, replacing the usual anion, chloride, with a chaotropic anion, usually nitrate. We phosphorylated enzyme from canine kidney with [32P]ATP. We estimated interconversion rate constants for the reaction E1P ⇌ E2P and their ratio. To estimate rate constants we terminated phosphorylation and observed decay kinetics. We observed E1P or E2P selectively by adding K+ or ADP respectively. K+ dephosphorylates E2P leaving E1P as observable species; ADP dephosphorylates E1P leaving E2P as observable species. We fitted a 2-pool model comprising two reactive species or a twin 2-pool model, comprising a pair of independent 2-pool models, to the data and obtained interconversion and hydrolysis rate constants for each state. Replacing Na+ with Tris+ or lysine+ did not change the ratio of interconversion rate constants between E1P and E2P. Thus Na+ binds about equally strongly to E1P and E2P. This conclusion is consistent with a model of Pedemonte (1988. J. Theor. Biol. 134:165–182.). We found that Na+ affected another equilibrium, that of transphosphorylation between ATP·dephosphoenzyme and ADP·E1P. We used the reactions and model of Pickart and Jencks (1982. J. Biol. Chem. 257:5319–5322.) to generate and fit data. Decreasing the concentration of Na+ 10-fold shifted the equilibrium constant 10-fold favoring ADP·E1P over ATP·dephosphoenzyme. Thus Na+ can dissociate from E1P·Na3. Furthermore, we found two characteristics of Hofmeister effects on this enzyme.

Rate constants, timescales, and free energy barriers

2016 ◽  
Vol 41 (1) ◽  
Author(s):  
Peter Salamon ◽  
David Wales ◽  
Anca Segall ◽  
Yi-An Lai ◽  
J. Christian Schön ◽  
...  
Keyword(s):  
Free Energy ◽  
Transition State ◽  
Rate Constants ◽  
Transition State Theory ◽  
State Theory ◽  
Energy Landscapes ◽  
Energy Barriers ◽  
Free Energy Landscapes

AbstractThe traditional connection between rate constants and free energy landscapes is extended to define effective free energy landscapes relevant on any chosen timescale. Although the Eyring–Polanyi transition state theory specifies a fixed timescale of

Ab initio determination of the energy barriers and rate constants for HOBO+HF→FBO+H2O and OBBO+HF→FBO+HBO

1995 ◽  
Vol 103 (19) ◽  
pp. 8538-8543 ◽  
Author(s):  
Douglas P. Linder ◽  
Michael Page
Keyword(s):  
Ab Initio ◽  
Rate Constants ◽  
Energy Barriers
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