Homogeneous activation energy

Data of chemical composition 106 Pressure changes 145 Variables related to composition 164 Half iife and initial rate data 177 Temperature variation. Activation energy Homogeneous catalysis 202 Enzyme and solid catalysis 210 Flow reactor data 222 CSTR data 231 Complex reactions 238... 

A homogeneous catalyst is one that is present in the same phase as the reactants. It speeds up the reaction by forming a reactive intermediate that decomposes to give products. In this way, the catalyst provides an alternative process of lower activation energy. 

Let us consider a surface on which particles are adsorbed on sites with different activation energy of desorption, and the distribution of these energies over the surface is discrete so that ni0 particles are initially in a state with an activation energy of desorption Edt, n particles with an energy Ed/, etc. Such a model corresponds to a concept of adsorption on different crystal planes each of which is homogeneous, or to a concept of different adsorption states of the particles adsorbed on a single crystal (26, 88). 

It is apparent, from the above short survey, that kinetic studies have been restricted to the decomposition of a relatively few coordination compounds and some are largely qualitative or semi-quantitative in character. Estimations of thermal stabilities, or sometimes the relative stabilities within sequences of related salts, are often made for consideration within a wider context of the structures and/or properties of coordination compounds. However, it cannot be expected that the uncritical acceptance of such parameters as the decomposition temperature, the activation energy, and/or the reaction enthalpy will necessarily give information of fundamental significance. There is always uncertainty in the reliability of kinetic information obtained from non-isothermal measurements. Concepts derived from studies of homogeneous reactions of coordination compounds have often been transferred, sometimes without examination of possible implications, to the interpretation of heterogeneous behaviour. Important characteristic features of heterogeneous rate processes, such as the influence of defects and other types of imperfection, have not been accorded sufficient attention. 

The kinetics of resole cure reactions monitored via FTIR suggest that a diffusion mechanism dominates below 140°C. The cure above 140°C exhibits a homogeneous first-order reaction rate. The activation energy of the cure reaction was -"-49.6 kJ/mole.66... 

Catalysts participate in reactions but are not themselves used up they provide a reaction pathway with a lower activation energy. Catalysts are classified as either homogeneous or heterogeneous. 

In a further step, an extended kinetic model was developed and applied, considering the kinetics of the homogeneous side reactions as well [94]. By this means, the activation energies of these processes could be derived. 

Indeed, assuming that the surface of adsorbent is characterized by homogeneous distribution in adsorption activation energy we arrive to the Zeldovich - Roginsky - Elovich kinetic isotherm of In (f + + providing the validity of function (2.50) in case of direct in-... 

A different situation arises with a preliminary reduced surface. In this case the measured value of y is within lO - 10 2, and as the temperature increases, the y grows by the Arrhenius Law (Equation) with the activation energy of 5.2 kcal/mole. In addition, there is dependence of y upon the triplet oxygen pressure in the set-up, though the experiment conditions allow us to neglect a priori the impact of homogeneous processes on the spatial distribution of 02( A ) molecules. Prolonged... 

The rates of certain reactions of polymers have been reported to be enhanced by MW under homogeneous conditions at atmospheric pressure. Lewis et al. [64] performed kinetic studies on the imidization of the polymer BDTA-DDS polyamic acid 46 in N-methylpyrrolidone (NMP) giving the polymer 47 (Scheme 4.24) and showed that the apparent activation energy was reduced from 105 kj mol-1 under conventional heating to 55 kj mol-1 under MW heating. Rate enhancements (kMw/kthermai)... 

It has been shown [90] that the homogeneous dissociation of methane is the only primary source of free radicals and it controls the rate of the overall process. This reaction is followed by a series of consecutive and parallel reactions with much lower activation energies. After the formation of acetylene (C2H2), a sequence of very fast reactions occurs, leading to the production of higher unsaturated and aromatic hydrocarbons and finally carbon ... 

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