Enthalpies of formation of monoderivatives of hydrocarbons: Interaction of polar groups with an alkyl group

2004 ◽  
Vol 25 (16) ◽  
pp. 1979-1986 ◽  
Author(s):  
Otto Exner ◽  
Stanislav Böhm
Keyword(s):  
Alkyl Group ◽  
Enthalpies Of Formation ◽  
Polar Groups

Interaction of Polar Groups with a Bulky Hydrocarbon Residue: Polarizability and Steric Effects

2005 ◽  
Vol 70 (3) ◽  
pp. 370-382 ◽  
Author(s):  
Stanislav Böhm ◽  
Otto Exner
Keyword(s):  
Steric Effect ◽  
Extreme Case ◽  
Steric Effects ◽  
Enthalpies Of Formation ◽  
Straight Chain ◽  
Polar Groups ◽  
Sterically Demanding ◽  
Additive Rule ◽  
Stabilization Energies ◽  
The Individual

Energies of two series of branched hydrocarbon monosubstituted derivatives, 2-substituted 2-methylpropanes and 1-substituted bicyclo[2.2.2]octanes with 19 different substituents were calculated at the B3LYP/6-311+G(d,p) level and compared with the energies of straight-chain 1-substituted butanes. The comparison was carried out in terms of isodesmic homodesmotic reactions, in which the substituent is transferred from one hydrocarbon residue to another. The branched derivatives are mostly stabilized, in the extreme case by as much as 30 kJ mol-1 confirming that the additive rule used for estimating the enthalpies of formation is not valid for branched derivatives. The stabilization energies ∆E for the individual substituents X are not proportional to any known substituent parameters. In the qualitative respect, they are controlled by the first atom of the substituent - similarly as in the straight-chain isomers - but in the case of sterically demanding substituents they are perturbed by a destabilizing steric effect.

Microscopic versus process parameters in heavy-oil upgrading

1992 ◽  
Vol 50 (1) ◽  
pp. 366-367
Author(s):  
V.A. Munoz ◽  
R.J. Mikula ◽  
C. Payette ◽  
W.W. Lam
Keyword(s):  
Molecular Weight ◽  
Liquid Fuels ◽  
Chemical Components ◽  
Heavy Oils ◽  
Synthetic Fuels ◽  
High Hydrogen ◽  
Optical Texture ◽  
Polar Groups ◽  
Anisotropic Character ◽  
Planar Molecules

The transformation of high molecular weight components present in heavy oils into useable liquid fuels requires their decomposition by means of a variety of processes. The low molecular weight species produced recombine under controlled conditions to generate synthetic fuels. However, an important fraction undergo further recombination into higher molecular weight components, leading to the formation of coke. The optical texture of the coke can be related to its originating components. Those with high sulfur and oxygen content tend to produce cokes with small optical texture or fine mosaic, whereas compounds with relatively high hydrogen content are likely to produce large optical texture or domains. In addition, the structure of the parent chemical components, planar or nonplanar, determines the isotropic or anisotropic character of the coke. Planar molecules have a tendency to align in an approximately parallel arrangement to initiate the formation of the nematic mesophase leading to the formation of anisotropic coke. Nonplanar highly alkylated compounds and/or those rich in polar groups form isotropic coke. The aliphatic branches produce steric hindrance to alignment, whereas the polar groups participate in cross-linking reactions.

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

Reduction of terphenyl iron(ii) or cobalt(ii) halides in the presence of trimethylphosphine: an unusual triple dehydrogenation of an alkyl group

2009 ◽  
pp. 5401 ◽  
Author(s):  
Chengbao Ni ◽  
Bobby D. Ellis ◽  
Troy A. Stich ◽  
James C. Fettinger ◽  
Gary J. Long ◽  
...  
Keyword(s):  
Alkyl Group

scholarly journals MW irradiation and ionic liquids as green tools in hydrolyses and alcoholyses

2020 ◽  
Vol 10 (1) ◽  
pp. 001-010 ◽  
Author(s):  
Nikoletta Harsági ◽  
Betti Szőllősi ◽  
Nóra Zsuzsa Kiss ◽  
György Keglevich
Keyword(s):  
Ionic Liquids ◽  
Alkaline Hydrolysis ◽  
Alkyl Group ◽  
Phosphinic Acid ◽  
Reaction Times ◽  
Alternative Possibility ◽  
First Order ◽  
Pseudo First Order ◽  
Mw Irradiation ◽  
Hydrolysis Of

Abstract The optimized HCl-catalyzed hydrolysis of alkyl diphenylphosphinates is described. The reaction times and pseudo-first-order rate constants suggested the iPr > Me > Et ∼ Pr ∼ Bu order of reactivity in respect of the alkyl group of the phosphinates. The MW-assisted p-toluenesulfonic acid (PTSA)-catalyzed variation means a better alternative possibility due to the shorter reaction times, and the alkaline hydrolysis is another option. The transesterification of alkyl diphenylphosphinates took place only in the presence of suitable ionic liquids, such as butyl-methylimidazolium hexafluorophosphorate ([bmim][PF6]) and butyl-methylimidazolium tetrafluoroborate ([bmim][BF4]). The application of ethyl-methylimidazolium hydrosulfate ([emim][HSO4]) and butyl-methylimidazolium chloride ([bmim][Cl]) was not too efficient, as the formation of the ester was accompanied by the fission of the O–C bond resulting in the formation of Ph2P(O)OH. This surprising transformation may be utilized in the phosphinate → phosphinic acid conversion.

scholarly journals Construction of the Cellulose Nanofibers (CNFs) Aerogel Loading TiO2 NPs and Its Application in Disposal of Organic Pollutants

Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1841
Author(s):  
Kang Li ◽  
Xuejie Zhang ◽  
Yan Qin ◽  
Ying Li
Keyword(s):  
High Efficiency ◽  
Sol Gel ◽  
Cellulose Nanofibers ◽  
Three Dimensional ◽  
Good Mechanical Property ◽  
Polar Groups ◽  
Dimensional Network ◽  
Natural Polysaccharide ◽  
Valuable Method ◽  
Adsorption Capability

Aerogels have been widely used in the adsorption of pollutants because of their large specific surface area. As an environmentally friendly natural polysaccharide, cellulose is a good candidate for the preparation of aerogels due to its wide sources and abundant polar groups. In this paper, an approach to construct cellulose nanofibers aerogels with both the good mechanical property and the high pollutants adsorption capability through chemical crosslinking was explored. On this basis, TiO2 nanoparticles were loaded on the aerogel through the sol-gel method followed by the hydrothermal method, thereby the enriched pollutants in the aerogel could be degraded synchronously. The chemical cross-linker not only helps build the three-dimensional network structure of aerogels, but also provides loading sites for TiO2. The degradation efficiency of pollutants by the TiO2@CNF Aerogel can reach more than 90% after 4 h, and the efficiency is still more than 70% after five cycles. The prepared TiO2@CNF Aerogels have high potential in the field of environmental management, because of the high efficiency of treating organic pollutes and the sustainability of the materials. The work also provides a choice for the functional utilization of cellulose, offering a valuable method to utilize the large amount of cellulose in nature.

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