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Effects on Chemical Reactions

Lemmetyinen, L. Lehtinen, and J. Koskikallio, Finn. Chem. Lett., 1979, 72 Chem. Abstr., 1980, 92, 5901). [Pg.368]

C-allylation of PhO Na with H2C=CHCH2C1 in a variety of solvents in the presence of different crown ethers is most effective in each case when using poly(vinylbenzo-15-crown-5)polyether. Only in the presence of the crown ethers 15-crown-5 and 18-crown-6 are the anions in potassium phthalimide and sodium saccharinate, respectively, sufficiently activated to bring about nucleophilic aromatic substitution of the 4-fluorine in pentafluoropyridine. The formation of 2,4-dinitrophenol, in addition to the expected ether, from 2,4-dinitrochlorobenzene and potassium 2-propoxide in 2-propanol-benzene (1 1), in the presence of dicyclohexyl-18-crown-6 polyether, has been accounted for on the basis of a nucleophile-radical reaction (5rn1)/  [Pg.369]

The double elimination of HHal from 1,1- and 1,2-dihalogeno-alkanes to give alkynes (terminal and internal) under very mild conditions is preparatively very simple in petroleum ether, using solid KOBu and catalytic amounts of 18-crown-6 polyether.Different transition-state structures within the E2 mechanism, as well as different initial-state solvation conditions, have been proposed to rationalize the effects of equimolar amounts of crown ether and base on the dehydrochlorination of (p-ClC6H4)2CH2CH(3 x)Ch (x = 1, 2, or 3).  [Pg.369]

15- Crown-5 and 18-crown-6 polyethers caused decreases in the rate constants of the dehydrochlorination with EtO , but increases with Bu 0 (by factors of [Pg.369]

16— 91, respectively). The orientation in 1,2-eliminations from 2-iodobutane that are caused by a variety of nitrogen and carbon bases in DMSO, with the counter-ion of the base being varied from Na to K , and then to in the presence of 18-crown-6, has revealed that ion pairing is important with the stronger anilide bases that were examined (e.g. that from m-chloroaniline) and especially with the sodium salts from Mc2S02 and MeS02Ph. In each case, the relative proportion of terminal alkene is smaller than when the base is freely dissociated. [Pg.369]


C. J. Collins and N. S. Borman, eds.. Isotope Effects on Chemical Reactions, Van Nusirand Reinhold, New York, 1970. [Pg.249]

K. Rietema, Segregation in Liquid-Liquid Dispersions and Its Effect on Chemical Reactions... [Pg.342]

The rate of burning of a propellant is also influenced by the initial temperature of the charge. The effect is much less than the normal effect on chemical reactions, but can still be important when the material is to be used over a wide range of temperatures from arctic to tropical and those encountered in supersonic flight. [Pg.181]

What was the importance of this research result for the chirality problem One difficulty is provided by the fact that the interaction responsible for the violation of parity is in fact not so weak at all, although it only acts across a very short distance (smaller than an atomic radius). Thus, the weak interaction is not noticeable outside the atomic nucleus, except for p-decay. It would thus have either no influence on chemical reactions or only a very limited effect on chemical reactions, as these almost completely involve only interactions between the electron shells. [Pg.249]

Before considering the analysis of solvent effects on chemical reactions, some of the shortcomings of potential energy hypersurfaces as a tool to describe chemical process are... [Pg.283]

Surrounding Medium Effects on Chemical Reactions Catalysis... [Pg.329]

Tapia, O. and Lluch, J. M. Solvent effects on chemical reaction profiles. Monte Carlo simulation of hydration effects on quantum chemically calculated stationary structures, J. Chem.Phys., 83 (1983, 3970-3982... [Pg.356]

The scope of this book goes beyond the proper field of solvent effects on chemical reactions. It actually goes deeper in the analysis of solvent effects as such and of chemical reactions. It also addresses the problem of mimicking chemical reactions in condensed phases and bioenvironments. The authors have gone through the problems raised by the limitations found in the theoretical representations. In order to understand, it is not sufficient to have agreement with experiments, the schemes should meet the requirements put forward by well founded physical theories. [Pg.387]

Abstract This chapter describes a number of examples of kinetic isotope effects on chemical reactions of different types (simple gas phase reactions, Sn2 and E reactions in solution and in the gas phase, a and 3 secondary isotope effects, etc.). These examples are used to illustrate many aspects of the measurement, interpretation, and theoretical calculation of KIE s. The chapter concludes with an example of an harmonic semiclassical calculation of a kinetic isotope effect. [Pg.313]

Ibrahim, S. S., R. W. Bilger, and N. R. Mudford, Turbulence Effects on Chemical Reactions in Smog Chamber Flows, Atmos. Environ., 21, 2609-2621 (1987). [Pg.936]

Catalysts and their effects on chemical reactions aid in efficiency, effectiveness and selectivity. A recent example of current research is redox and ligand exchange reactions of the oxygenation catalyst (N,N -bis(salicylidene)ethylenediaminato)co-balt(II), Co(SALEN)2 (below), and its one-electron oxidation product, Co(salen) 2-These were investigated in DMF, pyridine, and mixtures of these solvents. Solvent effects on the potentials, the thermodynamics of cross reactions, and the distribution of Co(II) and Co(III) species as a function of the solvent composition are important considerations (Eichhorn, 1997). The results in these solvents should be compared with other work with catalysts using more environmentally benign media (Collins et al., 1998). [Pg.28]

Contemporary computer-assisted molecular simulation methods and modern computer technology has contributed to the actual numerical calculation of solvent effects on chemical reactions and molecular equilibria. Classical statistical mechanics and quantum mechanics are basic pillars on which practical approaches are based. On top of these, numerical methods borrowed from different fields of physics and engineering and computer graphics techniques have been integrated into computer programs running in graphics workstations and modem supercomputers (Zhao et al., 2000). [Pg.285]

The classification of solvents has been dealt with in various books on non-aque-ous solvents [25, 26]. In the classification of solvents, it is usual to use some solvent properties as criteria. In order to discuss solvent effects on chemical reactions, it is convenient to use relative permittivities and acid-base properties as the criteria. [Pg.22]

As described above, the role of ion solvation is crucial in the dissolution of electrolytes. Ion solvation also has significant effects on chemical reactions and equilibria. Ion-solvent interactions that may participate in ion solvation are shown in Table 2.3 [8],... [Pg.30]

The various factors that contribute to ion solvation were discussed in Section 2.2.1. In this section, we deal with the solvent effects on chemical reactions more quantitatively [5, 22]. To do this, we introduce two quantities, the Gibbs energy of transfer and the transfer activity coefficient. [Pg.41]

We can use the transfer activity coefficients to predict solvent effects on chemical reactions and equilibria [22]. Some examples are shown below. [Pg.45]

Small amounts of impurities in solvents usually do not have serious effects on the physical properties of solvents (Section 2.5). However, they often have drastic effects on the chemical properties of solvents, changing the reaction mechanisms or making electrochemical measurements impossible. The extent of the effect of an impurity differs considerably, depending on the properties of the impurity and those of the solvent in which it exists. Impurities that have significant effects on chemical reactions or on electrochemical measurements are called reactive impurities. [Pg.288]

SEGREGATION IN LIQUID-LIQUID DISPERSIONS AND ITS EFFECT ON CHEMICAL REACTIONS... [Pg.237]

It was commented that In most reactions of complex molecules the intermediate has many more degrees of freedom and so the tendency will be to spend more time near the intermediate potential minimum and, thereby, to lose the directional information in the trajectory , but the model simulation certainly displays a possible role of dynamics effect on chemical reaction. [Pg.176]

Sonochemistry is defined as the chemical effects produced by ultrasonic waves. Ultrasound, with frequencies roughly between 15 kHz and 10 MHz, has a drastic effect on chemical reactions. It is the most important... [Pg.438]


See other pages where Effects on Chemical Reactions is mentioned: [Pg.843]    [Pg.883]    [Pg.284]    [Pg.285]    [Pg.390]    [Pg.313]    [Pg.316]    [Pg.322]    [Pg.324]    [Pg.328]    [Pg.338]    [Pg.342]    [Pg.149]    [Pg.285]    [Pg.439]    [Pg.90]   


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