Kinetic analysis tions

Zhu J, Sevilla MD (1990) Kinetic analysis of free-radical reactions in the low-temperature autoxida-tion of triglycerides. J Phys Chem 94 1447-1452... 

When an RA2 monomer reacts with the substitution effect then the appUca-tion of kinetics analysis will lead to a different molecular distribution to that resulting from a simple statistical analysis. This was convincingly demonstrated... 

Moreover, the reaction of methyl acrylate and N nosylbenzaldimine, which was promoted by DABCO in the absence of la, was homogeneous in CHCI3 and proved amenable to kinetic analysis. The reaction was monitored by GC analysis, and was found to display a first order kinetic dependence on both DABCO and methyl acrylate. In contrast to the MBH reaction, rate saturation with respect to the imine electrophile was observed. A prominent primary kinetic isotope effect was also observed ka/ko = 3.81) by comparison of initial reaction rate of methyl acrylate with separate reactions of a deuterio methyl acrylate, strongly suggesting that deprotona tion of the a H(D) was rate limiting. 

Freyer, M. W., Lewis, E. A. (2008). Isothermal titration calorimetry experimental design, data analysis, and probing macromolecule/ligand binding and kinetic inteac-tions. Methods Cell Biol., 84, 79-113. 

Obserx ations of rtidical intermediates by ESR or uv-vis spectroscopy like the observation of cycli/ti-tion of radictil probes indicate a homolytic rcttc-tion mechanism. A quantitative kinetic analysis is. however, required to revettl the impoilancc of the radical route. 

The inclusion of all these steps hopelessly complicates the kinetic equa tions which may be written but cannot be solved in general, though with partial simplification some analysis is possible. For details the reader is referred to textbooks on polymer kinetics. 

The mechanism of anionic polymerization of cyclosiloxanes has been the subject of several studies (145,146). The first kinetic analysis in this area was carried out in the early 1950s (147). In the general scheme of this process, the propaga-tion/depropagation step involves the nucleophilic attack of the silanolate anion on the silicon, which results in the cleavage of the siloxane bond and formation of the new silanolate active center (eq. 18). 

Wavefront analysis, a dynamic method for kinetic investiga-tions... 

Kinetic analysis of the polymer crystallization by the DSC method in isothermal conditions can provide information about the effect of nanoparticles on the mechanism of nucleation and crystals growth. The reduction of the half-crystalliza-tion time ti/2) was considered an evidence of the crystallization rate of polypropylene (PP) at low OMMT contents [35]. ti/2 was lower than that of neat polymers for the crystallization process of many polymer matrices modified with OMMT [36,37]. 

KINALC CHEMKIN based program for Kinetic aNALysis. http //garfield.chtan.elle.hn/Combus tion/kinalc.htm. 

Detailed kinetic analysis and 0-exchange experiments performed in [20] allowed evaluating the mechanism of the encaged Nazarov cycliza-tion shown in Scheme 5.20. It includes reversible encapsulation, protonation, and water loss from substrate, followed by irreversible electrocy-clization. Although the electrocyclization is a... 

Correlations of nucleation rates with crystallizer variables have been developed for a variety of systems. Although the correlations are empirical, a mechanistic hypothesis regarding nucleation can be helpful in selecting operating variables for inclusion in the model. Two examples are (/) the effect of slurry circulation rate on nucleation has been used to develop a correlation for nucleation rate based on the tip speed of the impeller (16) and (2) the scaleup of nucleation kinetics for sodium chloride crystalliza tion provided an analysis of the role of mixing and mixer characteristics in contact nucleation (17). Pubhshed kinetic correlations have been reviewed through about 1979 (18). In a later section on population balances, simple power-law expressions are used to correlate nucleation rate data and describe the effect of nucleation on crystal size distribution. 

ESR spectra for, 22 294, 301 as high-energy fuels, 18 2-4 hydrogenation course of, 18 6-8 equilibria, 18 7, 8 kinetic processes, 18 6, 7 experimental procedures, 18 19, 20 apparatus and methods, 18 20 materials, 18 20 mechanism of, 18 21-45 formation of isomeric decahydro-naphthalenes, 18 23-30 deuterogena-tion of - -octalin, 18 29 routes to trans isomers, 18 26-30 selectivity to trons-decalin, 18 24, 25 olefin intermediates, 18 30-45 dihydro-and hexahydronaphthalenes, 18 32, 33 analysis of products, 18 33 oc-tahydronaphthalenes, 18 34-45 analysis of products, 18 34 deu-... 

The electrode processes on the voltammetric and the preparative electrolysis time scales may be quite different. The oxidation of enaminone 1 with the hydroxy group in the ortho position under the controlled potential electrolysis gave bichromone 2 in 68% yield (Scheme 4.) with the consumption of 2.4 F/mol [21], The RDE voltammogram of the solution of 1 in CH3CN-O.I mol/1 Et4C104 showed one wave whose current function, ii/co C, was constant with rotation rates in the range from 1(X) to 2700 rpm and showed one-electron behavior by comparison to the values of the current function with that obtained for ferrocene. The LSV analysis was undertaken in order to explain the mechanism of the reaction which involves several steps (e-c-dimerization-p-deamina-tion). The variation of Ep/2 with log v was 30.1 1.8 mV and variation of Ep/2 with logC was zero. Thus, our kinetic data obtained from LSV compare favorably with the theoretical value, 29.6 mV at 298 K, for a first order rate low [15]. This observation ruled out the dimerization of radical cation, for... 

For chainwise polymerizations, the analysis of model systems implies consideration of the homopolymerization or copolymerization of bifunctional monomers. Kinetic results cannot be directly extrapolated to the case of networks, because very important features such as intramolecular cycliza-tion reactions are not present in the case of linear polymers. However, the nature of initiation and termination reactions may be assessed. For example, using electron spin resonance (ESR), Brown and Sandreczki (1990) identified different types of radicals produced during the homopolymerization of a monomaleimide (a model compound of bismaleimides). 

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