Kinetics and mechanism of zinc ferrite formation

The kinetics and mechanism of zinc ferrite formation are studied for pure oxide mixtures at temperatures up to 1000°C by X-ray analysis, DTA and chemical analysis. Formation of ferrite obeys a random nucleation equation with an activation energy of 29.4 kcal mole^?1 in the temperature range 635–780°C. The nucleation process is followed by formation of spinel in an ordered lattice at temperatures /s> 800°C. The possibility of ZnO dissolution in the ferrite is also considered for ZnO at ratios higher than equimolecular.     

Kinetics and mechanism for oxime formation from 2-quinolinecarboxaldehyde

Oxime formation from 2-quinolinecarboxaldehyde occurs with rate-limiting carbinolamine dehydration under both acidic and neutral conditions. Carbinolamine dehydration occurs via a transition state bearing a single positive charge, similar to the corresponding reaction for 2-pyridinecarboxaldehyde and unlike the same reaction for 2-, 3-, and 4-formyl-1-methylpyridinium ions and for the conjugate acids of 3- and 4-pyridinecarboxaldehydes. © 1996 John Wiley & Sons, Inc.     

Kinetics and mechanism of the formation of CO2 hydrate

This article proposes a mechanism of CO₂ hydrate formation taking into account both diffusion and reaction, and gives an analysis of its kinetics. The most important assumptions on the model are that water dissolves into liquid CO₂ and reacts to form CO₂ hydrate, and that the hydrate blocks the dissolution and diffusion of water. Computational simulations were conducted, and the model proposed explains well the many observations on the CO₂ hydrate formation in previous articles. It is concluded that liquid CO₂ disposed in a deep ocean will form a very thin film of CO₂ hydrate, and this will greatly control the CO₂ diffusion in the ocean. © 1993 John Wiley & Sons, Inc.     

Kinetics of diethyl sulfide oxidation by hydrogen peroxide and peroxymonocarbonate in the presence of surfactants

We have studied the effect of different surfactants on the rate of diethyl sulfide (Et₂S) oxidation by hydrogen peroxide and peroxymonocarbonate (HCO ₄ ^- ) in aqueous solutions. In all the studied cases, the rate of the reaction between Et₂S and H₂O₂ decreases as the surfactant concentration increases. The reaction of Et₂S with HCO ₄ ^- is catalyzed by cationic surfactants and inhibited by neutral and anionic surfactants.Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 40, No. 6, pp. 368–372, November–December, 2004.     

Kinetics and mechanism of formation of adhesive joints based on ethylene-vinyl acetate copolymers

The structure of transient zones in PVC-poly(ethylene-co-vinyl acetate), PET-poly(ethylene-co-vinyl acetate), and steel-poly(ethylene-co-vinyl acetate) adhesion systems is studied. It is shown that PET-poly(ethylene-co-vinyl acetate) and PVC-poly(ethylene-co-vinyl acetate) are related in incompatible and partially compatible systems, respectively. In the temperature range 100?C180°C, diffusion coefficients and the activation energy of diffusion are determined. The depth of penetration of copolymer macromolecules into the PVC phase is calculated. The kinetics of adhesive-joint formation is studied. For all systems, the increase in joint strength has a common character; for each temperature, the steady state is attained. The results are analyzed in terms of wetting and diffusion theories. Both models satisfactorily describe the kinetics of joint formation in compatible and incompatible systems (including steel-poly(ethylene-co-vinyl acetate). The effective activation energy of the kinetics of adhesive-joint formation is determined and compared with the activation energies of diffusion, the viscous flow of copolymers, the ?? transition, and the rate of conformation rearrangements in the surface layers of ethylene-vinyl acetate copolymers. It is suggested that the data obtained can be generalized in terms of the Bikerman theory of a ??weak boundary layer.??     

Electropolymerization : direct film formation on metal substrates-I: Kinetics and mechanism

Attempts have been made to produce, in situ, polymer films on tinplate cathodes by the electrolysis of conducting solutions of vinyl monomers for use in the can-lacquering industry. Study of a range of vinyl monomers revealed that film formation occurs at low monomer conversion only in the electrolysis of acrylonitrile and methacrylonitrile in NN'-dimethyl formamide. The highest rates of film formation were obtained by constant current electrolysis when tetraethyl ammonium p-toluene sulphonate (McKee Salt) was used as electrolyte. The rate of film formation increases with monomer concentration to a maximum and then falls rapidly. Chain propagation occurs by an anionic mechanism with ion pair formation favoured at high monomer concentrations. The physical properties of the coloured films produced rarely approach those required industrially and the method does not represent an alternative approach to the lacquering of food and beverage cans.     

5-Arylidene aminouracils: III. Kinetics and mechanism of sodium salts formation

It extension of the studies on the search for the new biologically active 5-aminouracyl derivatives, we synthesized by the reaction of dialkylphosphites with arylideneuracils respective aminomethylphosphonates. The high level of the antiviral and anti-mycobacterial activity of the target compounds correlates well with the physicochemical parameters characterizing their structure.     

Kinetics and mechanism of formation of isomeric 1-methyl- and 2-methyl-5-vinyltetrazoles

The alkylation of 5-(β-dimethylaminoethyl)tetrazole (1) with dimethyl sulfate afforded 5-(β-dimethylaminoethyl)-1-methyltetrazole (2) and 5-(β-dimethylaminoethyl)-2-methyltetrazole (3). The exhaustive alkylation of compounds 2 and 3 at the terminal dimethylamino group gave 1-methyl-(4) and 2-methyl-5-(β-trimethylammonioethyl)tetrazole (5) methyl sulfates. The proton elimination from the α-methylene (with respect to the tetrazole cycle) groups of the quaternary ammonium cations of salts 4 and 5 by the action of a base leads to the corresponding zwitterions 4 ^± and 5 ^±, which in the rate-determining step undergo the cleavage of the nitrogen—carbon bond with the formation of 1-methyl-5-vinyl- (6) and 2-methyl-5-vinyltetrazole (7). The true constant of the transformation of zwitterion 4 ^± into tetrazole 6 is 21 times higher than that for the transformation of zwitterion 5 ^± into tetrazole 7.     

Kinetics and mechanism of cyclodextrin inclusion complexation incorporating bidirectional inclusion and formation of orientational isomers

The kinetics of cyclodextrin (CD) inclusion complexation has been usually analyzed in terms of a one-step reaction or a consecutive two-step reaction involving intracomplex structural transformation as a second step. These schemes presume the inclusion of guest molecules through only one side of the CD cavity and the formation of unidirectional CD complexes. However, there has been increasing experimental evidence for the inclusion of guests through both sides of the CD cavity and the formation of orientational isomers for noncentrosymmetric guest molecules. This article presents a novel parallel reaction scheme for CD inclusion complexation, incorporating bidirectional inclusion and the formation of orientational isomers into the scheme. It is shown that the parallel reaction scheme gives the same concentration versus reaction time relationship as the consecutive two-step reaction scheme. The experimental methods for determining the microscopic directional rate constants are presented. The kinetic parameters of the two-step reaction scheme are expressed as functions of the directional rate constants. The ratios of orientational isomers of alpha-CD-based [2]-pseudorotaxanes and the microscopic directional rate constants of the threading and dethreading reactions are estimated from the reported thermodynamic and kinetics data obtained by using either the one-step or two-step reaction scheme. It is shown that the thermodynamic preference of an isomer over the other is mainly due to the slow dethreading rate of the isomer.     

Mechanism of sulfide oxidations by peroxymonocarbonate

A detailed mechanism for the oxidation of aryl sulfides by peroxymonocarbonate ion in cosolvent/water media is described. Kinetic studies were performed to characterize the transition state, including a Hammett correlation and variation of solvent composition. The results are consistent with a charge-separated transition state relative to the reactants, with an increase of positive charge on the sulfur following nucleophilic attack of the sulfide at the electrophilic oxygen of peroxymonocarbonate. In addition, an average solvent isotope effect of 1.5 +/- 0.2 for most aryl sulfide oxidations is consistent with proton transfer in the transition state of the rate-determining step. Activation parameters for oxidation of ethyl phenyl sulfide in tert-butyl alcohol/water are reported. From the pH dependence of oxidation rates and (13)C NMR equilibrium experiments, the estimated pK(a) of peroxymonocarbonate was found to be approximately 10.6.     

Kinetics and mechanism of enolization,diol formation,and decomposition of hexafluoroacetylacetone in aqueous solution

The rate constants of the enolization, diol formation and decomposition of hexafluoroacetylacetone were determined by UV-spectrometry in the temperature interval between 20 and 35°C. For each reaction the thermodynamic quantities of activation were calculated by the collision as well as the transition state theories and discussed in terms of the structural properties of the activated molecules and the reaction mechanisms.     

Kinetics of styrylquinolinc formation

A comprehensive kinetic investigation of reactions occurring in the formation of styryl-quinolines has been conducted. Specific rate data such as rate equations, rate constants, and thermodynamic activation values have been determined and utilized in a study of which factors are of greatest importance in the reactions forming 2-styrylquinolines. A mechanism has been proposed for the condensation reaction which agrees with rate relationships found. Gas-liquid partition chromatography was used to follow the kinetics of the condensation reactions. A rate constant of 5.41 × 10^?2M^?1min^?1 was found for the reaction of benzaldehyde with 2-methyl-quinoline using zinc chloride as a catalyst at 104.0°. Rate constants of 1.28 × 10^?2 MT^?1 min^?1 and 1.05 × 10^?2 M^?1 min^?1 were found for the reactions of p-methylbenzaldehyde and p-methoxybenzaldehyde with quinaldine to form 2-(p-methylstyryl)quinoline and 2-(p-methoxystyryl)-quinoline, respectively at 92.4°. A linear relationship was found using the Hammett equation. An Arrhenius plot was constructed from rate constants determined at five different temperatures for the reaction of benzaldehyde and quinaldine to form 2-styrylquinoline, using zinc chloride as a catalyst. The energy of activation, E_a, was found to be 22.2 kcal/mole for this reaction. The enthalpy of activation, ΔH?, free energy of activation, ΔF?, and entropy of activation, ΔS?, were found to be 21.4 kcal/mole, 27.7 kcal/mole and -16.7 eu/mole, respectively, at 104.0°. The mechanism proposed in the formation of 2-styrylquinoline involves the fast formation of a carbanion-zinc chloride complex, which then attacks, in the rate determining step, the aldehyde utilized in the reaction. The lack of reaction of certain methylquinolines is attributed to the inadequacy of the carbanion formed and not to the difficulty involved in the initial formation of the carbanion.     

Kinetics of vesicle formation

 The kinetics of vesicle formation from a hydrotrope (sodium xylenesulfonate) solution of a surfactant (Laureth 4) is studied by the use of a stopped-flow apparatus combined with a dynamic light scattering device to determine vesicle size in the system. The hydrotrope system studied presents a system with a high surfactant solubilization combined with vesicle formation simply by dilution with water. The kinetic results show a single exponential decay time. The kinetic analysis indicates that the vesicles are formed from a molecular solution which resulted from the shear in the stopped-flow device and grow by monomeric association. Received: 1 October 1996 Accepted: 22 November 1996     

Kinetics and mechanism of formation of polymeric products during the hydroxyalkylation of parabanic acid with oxiranes

The kinetics of the reaction between N‐(2‐hydroxyalkyl) hydroparabanates (HAHP) and N,N′‐bis(2‐hydroxyalkyl) parabanates (HAP) with ethylene and propylene oxides were studied. The addition of oxiranes to imide function of HAHP led to the formation of HAP. Further reaction of HAP with oxiranes resulted in trioxoimidazolidine ring opening and polymeric products. The kinetics of the system was studied in detail. Based on the final kinetic equations, the mechanism of the reactions was postulated. The temperature dependences of kinetic parameters and analytical data provided experimental evidences supporting the mechanism. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 399–406, 2006     

Kinetics and mechanism of the stepwise complex formation of Cu(II) with tren-centered tris-macrocycles

The stepwise complexation kinetics of Cu2+ with three tetratopic ligands L1, L2 and L3, tren-centred macrocycles with different bridges connecting the 14-membered macrocycles with the tren unit, have been measured by stopped-flow photodiode array techniques at 25 degrees C, I= 0.5 M (KNO3), and pH = 4.96. The reaction between the first Cu2+ and the ligand consists of several steps. In a rapid reaction Cu2+ first binds to the flexible and more reactive tren-unit. In this intermediate a translocation from the tren unit to the macrocyclic ring, which forms the thermodynamic more stable complex, takes place. This species can react further with a second Cu2+ to give a heterotopic dinuclear species with one Cu2+ bound by the tren-unit and the other coordinated by the macrocycle. A further translocation occurs to give the homoditopic species with two Cu2+ in the macrocycles. Finally a slow rearrangement of the dinuclear complex gives the final species. The rates of the translocation are dependent on the length and rigidity of the bridge, whereas the complexation rates with the tren unit are little affected by it. VIS spectra of the species obtained by fitting the kinetic results, EPR-spectra taken during the reaction, and ES mass spectra of the products confirm the proposed mechanism. The addition of a second, third and fourth equivalent of Cu2+ proceeds in an analogous way, but is complicated by the fact that we start and end with a mixture of species. These steps were evaluated in a qualitative way only.     

Kinetics and mechanism of coal flotation

 The flotation kinetics of coarse coal particles was studied in a modified version of the Hallimond tube at 25 °C using nitrogen as the carrier gas, in the pH range 2–12. The kinetics was followed by measuring the volume of the particles accumulated in the collector tube as a function of time. At each pH, the rate constants were determined at several buffer concentrations and were extrapolated to zero buffer concentration. The observed first-order rate constant was represented as the product of separable constants and functions such as f _D, f _V and f _pH, which depend only on the particle size, gas flow and the pH of the dispersion, respectively. The diameter, D, of the particles was in the range 505–127 μm. The observed rate constant decreased linearly with the diameter of the particles at constant flow and it was calculated that f _D=exp(−1.56D). The dependence of f _V on the flow is a consequence of the fact that the flotation occurs when a single particle is captured by two bubbles. f _V was shown to be independent of the particle diameter. The effect of the pH on the rate of flotation was considered as resulting from the adsorption of protons (or hydroxide ions) by the particles and bubbles through multiple equilibria, assuming that there is no interaction between the binding sites. The pH–rate profile showed that there were two species responsible for the flotation: one stable at pH below 5 and the other at high pH. Comparison of f _V, f _D and f _pH for the flotation of coal and pyrite allowed the prediction of the optimum conditions for the separation of mixtures of these particles by flotation. Received: 6 August 2001  Accepted: 19 September 2001