Distal Two-Bond versus Three-Bond Electronegative Oxo-Substituent Effect Controls the Kinetics and Thermodynamics of the Conversion of a C-Nitroso Function to the Corresponding Oxime in the Conformationally Locked Pentofuranose (Bicyclo[2.2.1]heptane) System

2014 ◽  
Vol 79 (16) ◽  
pp. 7266-7276 ◽  
Author(s):  
Mansoureh Karimiahmadabadi ◽  
Sayeh Erfan ◽  
Andras Földesi ◽  
Jyoti Chattopadhyaya
Keyword(s):  
Substituent Effect ◽  
Kinetics And Thermodynamics ◽  
Conformationally Locked

Scrutinizing the substituent effect on Mo-based electrocatalysts for molecular hydrogen release through axial–equatorial decomposition: a DFT study

2019 ◽  
Vol 21 (30) ◽  
pp. 16601-16614 ◽  
Author(s):  
Diana Yepes ◽  
Pablo Jaque ◽  
Jorge I. Martínez-Araya
Keyword(s):  
Substituent Effect ◽  
Molecular Hydrogen ◽  
Aqueous Media ◽  
Hydrogen Release ◽  
Dft Study ◽  
Kinetics And Thermodynamics

The effect of electron-donating and -withdrawing groups is studied in terms of axial and equatorial locations at the p-pyridine rings in the [(PY5Me2)MoO]2+ for the H2 release in aqueous media. It opens a way to modify its kinetics and thermodynamics.

Conformationally locked foldamers: Synthesis and properties of abiotic macrocycles

2020 ◽  
Author(s):  
Toyah Warnock ◽  
Peter Knipe
Keyword(s):  
Conformationally Locked

Adsorption of safranine T from aqueous medium by nano mesoporous MCM-41: adsorption equilibrium, kinetics, and thermodynamics

2020 ◽  
Vol 10 ◽  
Author(s):  
Xiao-Dong Li ◽  
Qing-Zhou Zhai
Keyword(s):  
Electron Microscopy ◽  
Ph Value ◽  
Particle Diameter ◽  
Spherical Particles ◽  
Practical Significance ◽  
Average Particle ◽  
Average Pore ◽  
Kinetics And Thermodynamics ◽  
Safranine T ◽  
Mcm 41

Introduction: In industrial production, a small amount of saffron T emissions will cause increase of water color and increase of chemical oxygen consumption, so study of the decolorization of saffron T wastewater has an important practical significance. Methods: MCM (Mobil Composition of Matter)-41 molecular sieve was synthesized by hydrothermal method. Power Xray diffraction and scanning electron microscopy were used to characterize the sample. Safranine T dye was adsorbed from water by the MCM-41 prepared. Kinetics and thermodynamics of the adsorption were studied. Results: The MCM-41 sample presented spherical particles and regular. The BET (Brunner-Emmett-Teller) specific surface area of the sample determined by 77 K low temperature nitrogen adsorption-desorption isotherm was 932 m2 /g. Its average particle diameter was 110 nm. TEM (transmission electron microscopy) results showed that the sample structure presented a honeycomb pore structure and the average pore diameter was 3.0 nm. The results showed that when room temperature was 20 ± 1 ℃, adsorbate safranine T: adsorbent MCM-41 = 20 : 1，the optimum pH value of adsorption was 4.0 and contact time was 20 min, the adsorption rate reached 98.29% and the adsorption capacity was 19.66 mg/g. The entropy change and enthalpy change of the adsorption system are respectively ΔS0 = 157.5 J/(mol·K); ΔH0 = 21.544 kJ/mol. When temperature was 277.15, 293.15, 303.15 K，the free energy change was respectively △G1 0 = -22.107 kJ/mol, △G2 0 = -24.627 kJ/mol, △G3 0 = -26.202 kJ/mol. Conclusion: The adsorption of safranine T by MCM-41 belongs to a pseudo-second-order adsorption. This adsorption accords with the Freundlich equation and belongs to a heterogeneous adsorption. The adsorption is an endothermic reaction of entropy increase, being spontaneous.

Substituent effect on wave numbers of C=O valence vibrations in ferrocene derivatives

1983 ◽  
Vol 48 (6) ◽  
pp. 1635-1646 ◽  
Author(s):  
Alexander Perjéssy ◽  
Štefan Toma
Keyword(s):  
Linear Correlation ◽  
Substituent Effect ◽  
Empirical Relation ◽  
Ferrocene Derivatives ◽  
Wave Numbers ◽  
Complex Structural ◽  
Transmission Factors

Wave numbers of C=O valence vibrations of 83 ferrocene derivatives have been measured in tetrachloromethane. For a series of 154 compounds containing ferrocene skeleton linear correlation has been found between wave numbers of C=O vibration and X+(R) constants of structural fragments in the sense of modified and extended Seth-Paul-Van Duyse equation. Validity has been verified of the recently derived empirical relation for calculation of the X+(R) constants of complex structural fragments from values of constants of substituents and transmission factors for simple structural groupings. The transmission factors γ and π' for 1,3- and 1,1'-ferrocene system have been found to be well applicable to calculation of constants of structural fragments containing ferrocene skeleton.

Ionic dimerisation of trifluoropropenenitrile and its addition reactions with methyl trifluoropropenoate

1980 ◽  
Vol 45 (2) ◽  
pp. 406-414 ◽  
Author(s):  
Jiří Svoboda ◽  
Oldřich Paleta ◽  
Václav Dědek
Keyword(s):  
Reaction Mechanism ◽  
Proton Transfer ◽  
Substituent Effect ◽  
Solvent Molecule ◽  
Addition Product ◽  
Potassium Fluoride ◽  
Relative Reactivity ◽  
Addition Reactions ◽  
Tertiary Amines ◽  
Optimum Conditions

Dimerisation of trifluoropropenenitrile (I) in the presence of potassium fluoride and tertiary amines afforded a mixture of stereoisomeric perfluoro-4-methyl-pentenedinitriles (II), higher-boiling compounds, and 2,3,3,3-tetrafluoropropanenitrile (III) which arises by proton transfer from the solvent molecule. Under optimum conditions, product II was obtained in about 50% yield. Reaction of the nitrile I with methyl trifluoropropenoate (IV) gave, besides the dimers II and V, the product of addition of the nitrile I to the propenoate, IV, i.e. methyl 4-cyanoperfluoro-2-pentenoate (VI), and the addition product of the propenoate IV to the nitrile I, i.e. methyl 4-cyanoperfluoro-2-methyl-3-butenoate (VII). The relative reactivity if I and IV is discussed. The ratio of stereoisomers in II, V, VI and VII indicates that the magnitude of the steric substituent effect, operating in the reaction mechanism, decreases in the order -CFCF3.(COOCH3) > -CFCF3(CN) > -COOCH3 > -CN.

Perturbation theory of substituent effect. Importance of the field effect in transmission of the substituent effect

1980 ◽  
Vol 45 (6) ◽  
pp. 1655-1661 ◽  
Author(s):  
Robert Ponec
Keyword(s):  
Perturbation Theory ◽  
Carboxylic Acids ◽  
Quantum Chemical ◽  
Substituent Effect ◽  
Field Effect ◽  
Adequate Description ◽  
Meta Position ◽  
Unsaturated Carboxylic Acids

Various quantum chemical approaches to the problem of transmission of the substituent effect were compared. It was shown that inclusion of the electronic repulsion (field effect) was necessary to give a true picture of differences in ρ constants for reactions of the cis and trans isomers of substituted unsaturated carboxylic acids; the same holds for an adequate description of transmission of the substituent effect from the meta position on a given skeleton.

Kinetic Study of Hydrolysis of Benzoates. Part XXVI. Variation of the Substituent Effect with Solvent in Alkaline Hydrolysis of Substituted Alkyl Benzoates

2006 ◽  
Vol 71 (11-12) ◽  
pp. 1557-1570 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Ilmar A. Koppel
Keyword(s):  
Kinetic Study ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Substituent Effect ◽  
Substituent Effects ◽  
Alkyl Substituent ◽  
Solvent Parameters ◽  
Substituent Constants ◽  
Hydrolysis Of ◽  
Main Factor

The second-order rate constants k2 (dm3 mol-1 s-1) for the alkaline hydrolysis of substituted alkyl benzoates C6H5CO2R have been measured spectrophotometrically in aqueous 0.5 M Bu4NBr at 50 and 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH, CH2C6H5, CH2CH2Cl, CH2CH2OCH3, CH2CH3) and in aqueous 5.3 M NaClO4 at 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH). The dependence of the alkyl substituent effects on different solvent parameters was studied using the following equations:      ∆ log k = c0 + c1σI + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆EσI + c7∆YσI + c8∆PσI     ∆ log k = c0 + c1σ* + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆Eσ* + c7∆Yσ* + c8∆Pσ* .  ∆ log k = log kR - log kCH3. σI and σ* are the Taft inductive and polar substituent constants. E, Y and P are the solvent electrophilicity, polarity and polarizability parameters, respectively. In the data treatment ∆E = ES - EH2O , ∆Y = YS - YH2O , ∆P = PS - PH2O were used. The solvent electrophilicity, E, was found to be the main factor responsible for changes in alkyl substituent effects with medium. When σI constants were used, variation of the polar term of alkyl substituents with the solvent electrophilicity E was found to be similar to that observed earlier for meta and para substituents, but twice less when σ* constants were used. The steric term for alkyl substituents was approximately independent of the solvent parameters.

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