Chemical reactions disproportionation

The basic idea of catalysis can be traced to the writings of J. J. Berzelius/ who in 1836 reviewed a number of curious occurrences in which traces of certain substances seemed to have an effect on chemical reactions disproportionate to then-amounts. In a passage often quoted, but bearing repetition, he wrote/- ... 

The assumption that k values are constant over the entire duration of the reaction breaks down for termination reactions in bulk polymerizations. Here, as in Sec. 5.2, we can consider the termination process—whether by combination or disproportionation to depend on the rates at which polymer molecules can diffuse into (characterized by kj) or out of (characterized by k ) the same solvent cage and the rate at which chemical reaction between them (characterized by kj.) occurs in that cage. In Chap. 5 we saw that two limiting cases of Eq. (5.8) could be readily identified ... 

Even though the chemical reactions are the same (i.e. combination, disproportionation), the effects of compartmentalization are such that, in emulsion polymerization, particle phase termination rates can be substantially different to those observed in corresponding solution or bulk polymerizations. A critical parameter is n, the average number of propagating species per particle. The value of h depends on the particle size and the rates of entry and exit. 

The photolysis of dimethyl sulphoxide (at 253.7 nm) in a wide range of solvents has been studied in detail176. Three primary reactions occur, namely (i) fragmentation into methyl radicals and methanesulphinyl radicals, equation (60), (ii) disproportionation into dimethyl sulphone and dimethyl sulphide, equation (61) and (iii) deactivation of the excited state to ground state dimethyl sulphoxide. All chemical processes occur through the singlet state. Further chemical reactions of the initial photochemical products produce species that have been oxidized relative to dimethyl sulphoxide. 

The relative importance of the disproportionation process (SET between two anion radicals) depends principally on the thermodynamic constant (K). It can be easily determined more or less accurately from the potential difference existing between the first cathodic peak and the second one. (An exact calculation would be possible from the thermodynamic potentials of the two reversible transfers in the absence of proton sources and at reasonable sweep rates so as to inhibit any undesirable chemical reaction.)... 

The number of chemical reactions used in CVD is considerable and include thermal decomposition (pyrolysis), reduction, hydrolysis, disproportionation, oxidation, carburization, and nitrida-tion. They can be used either singly or in combination (see Ch. 3 and 4). These reactions can be activated by several methods which are reviewed in Ch. 5. The most important are as follows ... 

Now consider the other extreme condition where diffusion is rapid relative to chemical reaction [i.e., hT( 1 — a) is small]. In this situation the effectiveness factor will approach unity for both the poisoned and unpoisoned reactions, and we must retain the hyperbolic tangent terms in equation 12.3.124 to properly evaluate Curve C in Figure 12.11 is calculated for a value of hT = 5. It is apparent that in this instance the activity decline is not nearly as sharp at low values of a as it was at the other extreme, but it is obviously more than a linear effect. The reason for this result is that the regions of the catalyst pore exposed to the highest reactant concentrations do not contribute proportionately to the overall reaction rate because they have suffered a disproportionate loss of activity when pore-mouth poisoning takes place. 

Second-order irreversible chemical reaction following a reversible electron transfer disproportionation. The disproportionation reaction can be represented as ... 

Chemical reactions are designated as C, so if the product of electron transfer undergoes a homogeneous chemical reaction we say that it is an EC reaction. The C terms are often given a superscript or subscript to show why type of chemical reaction occurs, e.g. disproportionation, dimerization or catalytic. Table 6.4 lists many of the commonly encountered Reinmuth terms. 

Disproportionation A chemical reaction in which a single compound serves as both an oxidizing and reducing agent. It converts to a more oxidized and a more reduced derivative. 

Transalliyiation. A chemical reaction involving the movement of a group from one molecule to another molecule, dealkylating the first, alkylating the second. An example would be the reaction in which two molecules of toluene form benzene and j -lene, which involves a quick two-step of a methyl group and a hydrogen between toluene molecules (also called disproportionation). 

The study of Li28 + DMF solutions [60] also allowed to characterize the electrochemical properties of polysulfides only redox couples of the type 8 /8 are involved. The chemical reactions coupled to charge transfers are classical dissociation and disproportionation equilibria no complex rearrangement reaction or transient species has been necessary. Redox potentials and charge-transfer coefficients of the redox couples involved in sulfur and polysulfide solutions are summarized in Table 2. 

E=electrochemical reaction, C=chemical reaction, and disp=disproportionation). 

This cascade however may be propagated throughout the cell unless terminated by a protective mechanism (see below) or a chemical reaction such as disproportionation, which gives rise to a non-radical product. Polyunsaturated fatty acids, found particularly in membranes, are especially susceptible to free radical attack. The effects of lipid peroxidation are many and various. Clearly, the structural integrity of membrane lipids will be adversely affected. In the lipid radical produced, the sites of unsaturation may change, thereby altering the fluidity of the membrane (see chap. 3). Lipid radicals may interact with other lipids and... 

A summary of the major chemical reactions of free radicals is given in Table 4.3. Broadly speaking these can be classified as unimolecular reactions of dissociations and isomerizations, and bimolecular reactions of additions, disproportionations, substitutions, etc. The complexity of many photochemical reactions stems in fact from these free radical reactions, for a single species formed in a simple primary process can lead to a variety of final products. 

As indicated in Chapter 1, principally, the reactions may be conjugated, when one of them slows another one down, and somewhat inhibits it. The mechanism of slowing down the secondary reaction may have different origins (e.g. if the target reaction is of the catalytic type, and intermediate products (IP) poisoning the catalyst are formed in the primary reaction). Another possible case is realized when IP of both reactions recombine or disproportionate (active sites are eliminated). Such negative effects of chemical reactions allow us to... 

In the case of brominated additives the process is less studied, for decabromodiphenyl oxide, a widely used brominated fire-retardant additive, Sb8OnBr2 is the dominant oxybromide, whereas Sb405Br2 was not detected in measurable amounts. It was assumed that, if this last is formed by bromination of Sb8OnBr2, it eliminates SbBr3 relatively rapidly either by thermal disproportionation or by chemical reaction with decabromodiphenyl oxide.42... 

The chemical reactions used in CVD are pyrolysis, hydrolysis, disproportionation, reduction, oxidation, carburization, and nitridization [16]. The selection of the precursors is regulated by general features that can be summarized as follows [17] stability at room temperature, enough volatility at low temperature, high purity, ability to react plainly on or with the support, and ability to react without the production of side or parasitic reactions. 

Plateau Pressure/Temperature Plateau Slope Hysteresis Heat of Reaction Hydrogen Capacity Volume Change Rate of Decrepitation Ease of Activation Kinetics of Reaction Tolerance to Gaseous Impurities Chemical Stability (Disproportionation)... 

Disproportionation. That type of chemical reaction in which some molecules of a single compound are oxidized and other molecules are reduced a reaction of the type 2A = B + <7, where B and C differ in degree of saturation or oxidation. 

We cannot, then, expect this approach to understanding chemical reactivity to explain everything. Most attempts to check the validity of frontier orbital theory computationally indicate that the sum of all the interactions of the filled with the unfilled orbitals swamp the contribution from the frontier orbitals alone. Even though the frontier orbitals make a weighted contribution to the third term of the Salem-Klopman equation, they do not account quantitatively for the many features of chemical reactions for which they seem to provide such an uncannily compelling explanation. Organic chemists, with a theory that they can handle easily, have fallen on frontier orbital theory with relief, and comfort themselves with the suspicion that something deep in the patterns of molecular orbitals must be reflected in the frontier orbitals in some disproportionate way. 

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