Kinetics disproportionation

In this section, the current-potential curves of multi-electron transfer electrode reactions (with special emphasis on the case of a two-electron transfer process or EE mechanism) are analyzed for CSCV and CV. As in the case of single and double pulse potential techniques (discussed in Sects. 3.3 and 4.4, respectively), the equidiffusivity of all electro-active species is assumed, which avoids the consideration of the influence of comproportionation/disproportionation kinetics on the current corresponding to reversible electron transfers. A general treatment is presented and particular situations corresponding to planar and nonplanar diffusion and microelectrodes are discussed later. 

Disproportionation equilibria have been studied for various systems. Cauquis and co-workers investigated by electrochemical means the matrix of equilibria corresponding to Scheme 2 for 3,7-dimethoxypheno-thiazine and its derivatives, and applied the measurement of the response of the equilibria to different conditions of basicity to the definition of a scale of basicity in acetonitrile. The disproportionation kinetics of the iron-thionine system were measured several years ago solvent effects on the disproportionation rate constant have been examined, and, lately, an indirect measurement of the synproportionation rate constant of thionine and leucothionine has been made. ... 

Reactions of carboxylates containing the more electropositive cations yield product carbonates, or sometimes the basic carbonates. Some of these salts, e.g., those of the alkali metals, melt before decomposition. The oxide products from decomposition of the lanthanide compounds may contain carbon deposited as a result of carbon monoxide disproportionation. Kinetic measurements must include due consideration of the possible retention of carbon dioxide by the product (as COj ) and the secondary reactions involved in carbon deposition. 

Initial experiments involved the use of hydroquinones, ascorbate and dihydroxy fumarate as substrates for the enzyme [120], Radicals (e.g., 5 and 6) were detected under steady-state conditions using a flow system to minimize substrate depletion. The narrow line spectra (Fig. 6a,b) of the radical anions are identical to those generated in chemical systems, indicating that the radicals are free in solution rather than associated with the enzyme. If it is assumed that the reaction proceeds by one-electron oxidation of the substrate and that the product radicals decay by self-reaction (e.g., disproportionation), kinetic analysis predicts that the steady-state radical... 

Disproportionation.—Disproportionation of, for instance, pent-2-ene to but-2-ene plus hex-3-ene, catalysed by MoCl2L2(NO)2 in the presence of alkylaluminium chlorides, occurs via rapid reversible formation of olefin complexes followed by rate-determining disproportionation. Kinetic results are reported, and the role of the metal discussed in terms of the requisite orbital transformations. ... 

In diluted solutions, the Ti(ll) intermediate is more stable, and also the disproportionation kinetics of Ti(l) can be detected. Total four-electron reduction to Ti(0) is observed with the formation of Ti(lll) and Ti(I) as the relatively stable intermediates. 

Gloss, G. L. and Redwine, O. D., Cychzation and disproportionation kinetics of triplet generated, medium chain length, localized biradicals measured by time-resolved CIDNP, J. Am. Chem. Soc. 107, 4543, 1985. 

The degree of polymerization in Eq. (6.41) can be replaced with the kinetic chain length, and the resulting expression simplified. To proceed, however, we must choose between the possibilities described by Eqs. (6.34) and (6.35). Assuming termination by disproportionation, we replace n, by v, using Eq. (6.37) ... 

Both monocalcium phosphate and dicalcium phosphate dissolve incongmently in water, disproportionating to more basic calcium phosphate and phosphoric acid. The extent of these reactions varies with the temperature and the amount of water. If water is added gradually to anhydrous monocalcium phosphate, equiUbrium conditions first correspond to a mixture of the anhydrous salt and its monohydrate. After conversion to the monohydrate, further reaction affords dicalcium phosphate plus free phosphoric acid. Dicalcium phosphate decomposes in aqueous solution to the more basic hydroxyapatite and phosphoric acid via intermediate octacalcium phosphate. The compHcated stepwise conversion of the acidic mono- and dicalcium phosphates to hydroxyapatite is summarized in equations 6—9. The kinetics are quite complex. 

The main reason that the decreases as the polymerization temperature increases is the increase in the initiation and termination reactions, which leads to a decrease in the kinetic chain length (Fig. 17). At low temperature, the main termination mechanism is polystyryl radical coupling, but as the temperature increases, radical disproportionation becomes increasingly important. Termination by coupling results in higher PS than any of the other termination modes. 

Equation 22 gives the maximum theoretical obtainable chlorine dioxide from the disproportionation of HCIO,. Experimentally, differences in the stoichiometry have been reported. This is because the chloride formed in equation 21 can catalyze the reaction to form more chlorine dioxide as in equation 22. Proposed mechanisms for these reactions and the kinetics under various conditions have been described (16,108). 

Entry 3 has only alkyl substituents and yet has a significant lifetime in the absence of oxygen. The tris(/-butyl)methyl radical has an even longer lifetime, with a half-life of about 20 min at 25°C. The steric hindrance provided by the /-butyl substituents greatly retards the rates of dimerization and disproportionation of these radicals. They remain highly reactive toward oxygen, however. The term persistent radicals is used to describe these species, because their extended lifetimes have more to do with kinetic factors than with inherent stability." Entry 5 is a sterically hindered perfluorinated radical and is even more long-lived than similar alkyl radicals. 

Anhydrous NaC102 crystallizes from aqueous solutions above 37.4° but below this temperature the trihydrate is obtained. The commercial product contains about 80% NaC102. The anhydrous salt forms colourless deliquescent crystals which decompose when heated to 175-200° the reaction is predominantly a disproportionation to C103 and Cl but about 5% of molecular O2 is also released (based on the C102 consumed). Neutral and alkaline aqueous solutions of NaC102 are stable at room temperature (despite their thermodynamic instability towards disproportionation as evidenced by the reduction potentials on p. 854). This is a kinetic activation-energy effect and, when the solutions are heated near to boiling, slow disproportionation occurs ... 

The modes of thermal decomposition of the halates and their complex oxidation-reduction chemistry reflect the interplay of both thermodynamic and kinetic factors. On the one hand, thermodynamically feasible reactions may be sluggish, whilst, on the other, traces of catalyst may radically alter the course of the reaction. In general, for a given cation, thermal stability decreases in the sequence iodate > chlorate > bromate, but the mode and ease of decomposition can be substantially modified. For example, alkali metal chlorates decompose by disproportionation when fused ... 

For all three halates (in the absence of disproportionation) the preferred mode of decomposition depends, again, on both thermodynamic and kinetic considerations. Oxide formation tends to be favoured by the presence of a strongly polarizing cation (e.g. magnesium, transition-metal and lanthanide halates), whereas halide formation is observed for alkali-metal, alkaline- earth and silver halates. 

Destruction of macroradicals—scission of kinetic chains. A disproportionation reaction is most common at this stage ... 

The disproportionation reaction destroys the layered structure and the two-dimensional pathways for lithium-ion transport. For >0.3, delithiated Li, AV02 has a defect rock salt structure without any well-defined pathways for lithium-ion diffusion. It is, therefore, not surprising that the kinetics of lithium-ion transport and overall electrochemical performance of Li, tV02 electrodes are significantly reduced by the transformation from a layered to a defect rock salt structure [76], This transformation is clearly evident from the... 

Purely parallel reactions are e.g. competitive reactions which are frequently carried out purposefully, with the aim of estimating relative reactivities of reactants these will be discussed elsewhere (Section IV.E). Several kinetic studies have been made of noncompetitive parallel reactions. The examples may be parallel formation of benzene and methylcyclo-pentane by simultaneous dehydrogenation and isomerization of cyclohexane on rhenium-paladium or on platinum catalysts on suitable supports (88, 89), parallel formation of mesityl oxide, acetone, and phorone from diacetone alcohol on an acidic ion exchanger (41), disproportionation of amines on alumina, accompanied by olefin-forming elimination (20), dehydrogenation of butane coupled with hydrogenation of ethylene or propylene on a chromia-alumina catalyst (24), or parallel formation of ethyl-, methylethyl-, and vinylethylbenzene from diethylbenzene on faujasite (89a). 

Knowledge of kui/kii is also important in designing polymer syntheses. For example, in the preparation of block copolymers using polymeric or multifunctional initiators (Section 7.6.1), ABA or AB blocks may be formed depending on whether termination involves combination or disproportionation respectively. The relative importance of combination and disproportionation is also important in the analysts of polymerization kinetics and, in particular, in the derivation of rate parameters. 

Berger and Mcycrhoff150 also reported that termination involves substantial disproportionation. They determined the initiator fragments per molecule in PS prepared with radiolabeled AIBN and conducted a detailed kinetic analysis of the system. They also found a marked temperature dependence for k k. Values of kt fkK ranged from 0.168 at 30 °C to 0.663 at 80 °C. 

GPC-derived weight average molecular weights are often less prone to error than number average molecular weights. When termination is wholly hy disproportionation or chain transfer and chains are long (>10 units), classical kinetics predicts Xn = XJ2 (Section 5.2.1.3). It follows that Cit can be obtained from the slope of a plot of 21 Xw vs [T]0/[M]t>."4 "5 The errors introduced even when the dominant process for radical-radical termination is combination (e.g. S polymerization) are small as long as X n is small in relation to... 

A wide range of nitroxidcs and derived alkoxyamincs has now been explored for application in NMP. Experimental work and theoretical studies have been carried out to establish structure-property correlations and provide further understanding of the kinetics and mechanism. Important parameters are the value of the activation-deactivation equilibrium constant K and the values of kaa and (Scheme 9.17), the combination disproportionation ratio for the reaction of the nilroxide with Ihe propagating radical (Section 9.3.6.3) and the intrinsic stability of the nitroxide and the alkoxyamine under the polymerization conditions (Section 9.3.6.4). The values of K, k3Cl and ktieact are influenced by several factors.11-1 "7-"9 ... 

ESI mass spectrometry ive mass spectrometry ESR spectroscopy set EPR spectroscopy ethyl acetate, chain transfer to 295 ethyl acrylate (EA) polymerizalion, transfer constants, to macromonomers 307 ethyl methacrylate (EMA) polymerization combination v.v disproportionation 255, 262 kinetic parameters 219 tacticity, solvent effects 428 thermodynamics 215 ethyl radicals... 

Few kinetic studies of the decompositions of these salts are available and, of those which have been investigated, the sulphites have received greatest attention. In general, sulphites disproportionate [803] in an inert atmosphere to sulphides and sulphates, the latter decomposing at a higher temperature. 

While there have been many non-isothermal studies of the decompositions of lanthanide oxalates, fewer detailed kinetic investigations have been reported. The anhydrous salts are difficult to prepare. La, Pr and Nd oxalates decompose [1097] to the oxide with intervention of a stable oxycarbonate, but no intermediate was detected during decomposition of the other lanthanide oxalates. The product CO disproportionates exten-... 

---