Kinetics of alkali-catalyzed m-cresol-formaldehyde reaction

The alkali-catalyzed reaction of m-cresol with formaldehyde carried out at 65°, 70°, 75° and 80°C and at pH 7, 8, 9, 9.4, and 10 follows second-order kinetics. The rate is found to increase with increase of pH. The overall rate constant (k) has been resolved into stepwise rate constants (k₁, k₂, and k₃) for the formation of monomethylol, dimethylol, and trimethylol cresol, respectively. For this purpose, the rate equations for the various possible steps have been given and the concentrations of the various methylol cresols formed determined. The experimental and calculated values of k at pH 10 and temperatures of 65°, 70°, and 80°C have been found to agree well within the experimental errors. Entropy of activation and the Arrhenius parameters for the overall reaction have also been calculated.     

Kinetics and mechanism of the alkali-catalyzed p-cresol–formaldehyde reaction

The kinetics of the reaction of p-cresol with formaldehyde in relation to the functionality of p-cresol using NaOH as catalyst has been studied at temperatures of (65 ± 0.05)°C, (70 ± 0.05)°C, (75 ± 0.05)°C, and (80 ± 0.05)°C. The pH maintained was 7.0, 8.0, 9.0, 9.4, and 10.0. The reaction follows a second-order rate law. The rate was found to increase with increase in pH. The stepwise rate constants (k₁ and k₂) for the formation of monomethylol-p-cresol and dimethylol-p-cresol, respectively, were calculated from the overall rate constant k. The values of Arrhenius parameters and the entropy of activation for the overall as well as the stepwise reactions were calculated. The experimental and calculated values of k at pH 10.0 and temperatures 65, 70, 75, and 80°C were found to agree well within experimental errors. A mechanism conforming to the energies and entropies of activation of the reaction is suggested.     

Kinetics of copolycondensation of bis(4-hydroxybutyl) terephthalate and bis(2-hydroxyethyl) terephthalate by ester-interchange reaction

The kinetics of polycondensation and copolycondensation reactions were investigated using bis(4-hydroxybutyl) terephthalate (BHBT) and bis (2-hydroxyethyl) terephthalate (BHET) as monomers. BHBT was prepared by ester interchange reaction of dimethyl terephthalate and 1,4-butanediol. BHBT and BHET were polymerized at 270°C in the presence of titanium tetrabutoxide (TBT) as a catalyst. Applying second-order kinetics for polycondensation, the rate constants of polycondensation of BHBT and BHET, k₁₁ and k₂₂, were calculated as 3.872 min⁻¹ and 2.238 min⁻¹, respectively. BHBT and BHET were also copolymerized at 270°C using TBT. The rate constants of crossreactions in the copolycondensation of BHBT and BHET, k₁₂ and k₂₁, were obtained by using the results obtained from a proton nuclear magnetic resonance (¹H-NMR) spectroscopy and a high-performance liquid chromatography (HPLC). It was found that the rate constants during the copolycondensation of BHBT and BHET at 270°C decreased in the order k₂₁ > k₁₁> k₂₂ > k₁₂ and the monomer reactivity ratio of BHBT was four or five times larger than that of BHET. In calculating the crossreactions, the method by the ¹H-NMR spectroscopy gave more accurate results than that by the HPLC. © 1996 John Wiley & Sons, Inc.     

A kinetic study on the autocatalytic cure reaction of a cyanate ester resin

The cure of a novolac‐type cyanate ester monomer, which reacts to form a polycyanurate network, was investigated by using differential scanning calorimeter. The conversions and the rates of cure were determined from the exothermic curves at several isothermal temperatures (513–553 K). The experimental data, showing an autocatalytic behavior, conforms to the kinetic model proposed by Kamal, which includes two reaction orders, m and n, and two rate constants, k₁ and k₂. These kinetic parameters for each curing temperature were obtained by using Kenny's graphic‐analytical technique. The overall reaction order was about 1.99 (m = 0.99, n = 1.0) and the activation energies for the rate constants, k₁ and k₂, were 80.9 and 82.3 kJ/mol, respectively. The results show that the autocatalytic model predicted the curing kinetics very well at high curing temperatures. However, at low curing temperatures, deviation from experimental data was observed after gelation occurred. The kinetic model was, therefore, modified to predict the cure kinetics over the whole range of conversion. After modification, the overall reaction order slightly decreased to be 1.94 (m = 0.95, n = 0.99), and the activation energies for the rate constants, k₁ and k₂, were found to be 86.4 and 80.2 kJ/mol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3067–3079, 2004     

Diffusion with simultaneous reaction of reactive dyes in cellulose. II. Effect of hydrolysis

Theoretical equations that describe the concentration profiles of immobilized and active species for reactive dyes were derived from the diffusion equation accompanied by the reaction with cellulose and water in the substrate. The diffusion coefficient D and the rate constant of the reaction with cellulose, k_cell, and that with water in cellulose, k_w, were estimated by using the theoretical equations and the cylindrical film roll method. The theory predicted that the apparent diffusion coefficients decreased with the hydrolysis of active species in cellulose. Results from diffusion experiments with C.I. Reactive Yellow 4 and Orange 1 show that the ratio P of k_w to k_cell for Orange 1 increased with increase in pH to about pH 13 and that the P for Yellow 4 was smaller than unity. Using an alternative experiment to diffusion, P of Orange 1 was measured to be 1.0–1.5, and that of Yellow 4 was smaller than unity at pH 11.6 at 30°C. It was therefore concluded that the D of active species was constant to a highly alkaline region and that the decrease in the apparent diffusion coefficient of Orange 1 was mainly due to the hydrolysis of active species in cellulose.     

The kinetics of the polymerization reaction of toluene diisocyanate with HTPB prepolymer

The uncatalysed and catalysed polymerization of a hydroxyl-terminated polybutadiene with toluene diisocyanate has been studied in toluene solution at four different temperatures. The rate constants (k₁, k₂) and the activation parameters (Ea₁, Ea₂, ΔS₁^?, ΔS₂^?) for the isocyanate groups in the 4 and 2 positions were calculated. It was found that the catalysts enhance the reactivity of the 2 position isocyanate group rather than the 4 position isocyanate group. It was also found that diethylcyclohexylamine has higher selectivity than dibutyltin dilaurate to enhance the reactivity of the isocyanate group in the 2 position. The effect of solvent has also been studied. The reactivity decreased in the following order; benzene = toluene > chlorobenzene > dioxane > nitrobenzene. © 1993 John Wiley & Sons, Inc.     

Kinetic study of the reaction between tocopheroxyl radical and unsaturated fatty acid esters in benzene

A kinetic study of the reaction between a tocopheroxyl radical and unsaturated fatty acid esters has been undertaken. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl oleate2, ethyl linoleate3, ethyl linolenate4, and ethyl arachidonate5) by the tocopheroxyl radical (5,7-diisopropyltocopheroxyl6) in benzene have been determined spectrophotometrically. The second-order rate constants, k₃, obtained are 1.04×10⁻⁵ M⁻¹s⁻¹ for2, 1.82×10⁻² M⁻¹s⁻¹ for3, 3.84×10⁻² M⁻¹s⁻¹ for4, and 4.83×10⁻² M⁻¹s⁻¹ for5 at 25.0°C. Thus, the rate constants, k_abstr/H, given on an available hydrogen basis are k₃/4=2.60×10⁻⁶ M⁻¹s⁻¹ for2, k₃/2=9.10×10⁻³ M⁻¹s⁻¹ for3, k₃/4=9.60×10⁻³ M⁻¹s⁻¹ for4, and k₃/6=8.05×10⁻³ M⁻¹s⁻¹ for5. The k_abstr/H values obtained for the polyunsaturated fatty acid esters3,4, and5 containing H-atoms activated by two π-electron systems are similar to each other, and are about three orders of magnitude higher than that for the ethyl oleate2 containing H-atoms activated by a single π-system. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils and fats may be induced by the above hydrogen abstraction reaction.     

Enantioselective hydrogenation of ethyl pyruvate over cinchonidine-Pt/Al2O3 catalyst. A reaction kinetic approach

A new reaction kinetic approach was used to describe the enantioselective hydrogenation of ethyl pyruvate over cinchona-Pt catalyst. The above reaction was considered as the sum of two parallel reactions: (i) racemic hydrogenation resulting in R- and S-product in equal amount and (ii) enantioselective hydrogenation leading to the exclusive formation of one of the two optically isomers. New terms such as acc_diff and k _e/k _r (where k _e and k _r are the rate constants of the enantioselective and racemic hydrogenation, respectively) were introduced to characterize the relationship between the enantioselective and the racemic hydrogenation reactions. Results obtained show that the formation of R-product is rate accelerated, while the formation of S-product is decelerated. The results indicate also that the overall rate increase is a kinetic phenomenon and cannot be attributed to the suppression of the poisoning effect of CO or oligomers formed from ethyl pyruvate. The strong rate acceleration effect of achiral tertiary amines (ATAs) added to the reaction mixture was attributed to the decrease of the loss of modifier during the hydrogenation experiments.     

Copolymerization of methyl methacrylate and allyl acetate Part I. Rate of reaction

Free radical bulk copolymerization of methyl methacrylate (MMA) and allyl acetate (AAc) has been investigated using electron spin resonance (ESR) and FT–near infrared (FTNIR) spectroscopy. Data are used to evaluate the rate constants. The mole fraction of AAc plays an important role in the copolymerization of these two monomers. AAc not only delays the Trommsdorff effect but also increases the onset of percentage total conversion at which the Trommsdorff region begins. With AAc fraction 0.5 and higher, no Trommsdorff effect was observed. Inclusion of AAc into copolymer structure mainly occurs in the Trommsdorf region or when the AAc fraction in the comonomer feed is dominant. This is associated with a drop in the concentration of propagating radicals. However, ESR spectra indicate that the MMA propagating radical is predominant during the reaction. In the comonomer mixtures where a Trommsdorff region can be observed, the addition of AAc does not produce any significant change in k_p and k_t in the steady state region. Major changes in k_p and k_t are observed after the gel point and glassy state, respectively. © 2001 Society of Chemical Industry     

Urethane reaction kinetics of butanediols catalyzed by Zr(acac)4

The urethane reaction of isocyanate was carried out with zirconium acetyl acetonate (Zr(acac)₄) as catalyst. 1,2‐Butanediol and 1,4‐butanediol were used as model compounds to investigate the reaction kinetics. It was shown that hydroxyl groups in 1,2‐butanediol appeared to have different reaction rate when reacting with phenyl isocyanate, which was labeled as k_fast and k_slow. It was very surprising that the reaction rate of 1,4‐butanediol (k_con) was very similar to the value of k_slow at the same temperature although there is only primary hydroxyl group in its molecule. Furthermore, activation energy (E_a), activation enthalpy (ΔH), and activation entropy (ΔS) for the reaction were calculated out, from which some catalytic properties of Zr(acac)₄ were revealed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Kinetics and mechanisms of reaction between carbon disulphide and morpholine in aqueous solutions

The reaction in aqueous solutions between carbon disulphide and morpholine has been studied experimentally at 303 K using a conductimetric stopped-flow technique. The observed pseudo-first order rate constant does not vary linearly with amine concentration but follows the equation: . This equation is compatible both with (i) zwitterion intermediate and (ii) single-step termolecular reaction mechanisms which were previously proposed for the corresponding reactions of CO₂ and COS. Values of rate constants k_Am and k_w at 303 K are also reported.     

Impedance investigation of the mechanism of copper electrodeposition from acidic perchlorate electrolyte

The mechanism of the copper electrodeposition from acidic perchlorate electrolyte has been investigated with polarization and impedance methods. The impedance of the copper electrode in copper perchlorate electrolytes has been measured as a function of frequency for different Edc overpotential values and different copper(II) ion concentrations. The relations between the shape of a complex plane impedance display and the copper electrode potential values as well as the concentration of CuII ion were analysed in terms of the electrode reaction mechanism. It is shown, that the presence of the intermediate cuprous ion and its sinusoidal change of transport rate is one of the main factors determining the depressed shape of the impedance arc. The quantitative relation between the faradaic impedance and the rates of electrode reaction rates was established. The impedance arc was simulated with a set of parameters involving: rate constants, Tafel slopes, diffusion coefficient of cuprous ion and double layer capacitance. The rate constants were calculated with respect to ECu2 + Cu00 as: k10 = 6.50 × 10−5 cm s−1, k20 = 0.139 cm s−1, k−20 = 1.88 × 10−7 mol cm−2 s−1.     

Radiation-induced polymerization of ethylene in pilot plant. IV. Kinetic analysis

The kinetics of the radiation-induced polymerization of ethylene in a flow system using tert-butyl alcohol aqueous solution as a medium were studied. The polymerization was carried out in a large-scale pilot plant with a 50-liter central source-type reactor at various mean residence times and does rates under constant pressure of 300 kg/cm², temperature of 30°C, and ethylene molar fraction of ca. 0.4. The reaction mixture in the reactor was back-mixed flow from the residual polymer concentration in the reactor. The results of the polymerization were analyzed by kinetic treatment based on a reaction mechanism with both first-and second-order terminations for the propagating radical. The apparent rate constants, except for that of second-order termination (k_t2), were consistent with those determined by small-scale batch experiments. The k_t2 is 20 to 40 times larger than that in the batch experiments. The k_t2 increases with decrease in mean residence time and with agitation, probably because of mobility of the propagating radical.     

Reactor engineering models of complex electrochemical reaction schemes. III. Galvanostatic operation of parallel reactions in batch reactors

Batch electrochemical reactor models for parallel reaction sequences are developed for cells operating galvanostatically. Independent and dependent parallel reactions and a parallel-series reaction scheme are considered and emphasis is placed on the development of analytical expressions to predict reactor behaviour. Electro-organic synthesis reactions such as the production of betaalanine and glyoxylic acid are considered as examples. Experimental data for the electro-oxidation of aqueous oxalic acid and glyoxylic acid solutions are shown to be in reasonable agreement with the reaction analysis.Nomenclature a Parameter defined in Equation 21 - C _j ^s Surface concentration of species j - C _j Bulk concentration of species j - C _jo Initial concentration of species j - C _Bmax Maximum concentration of species B - CE Current efficiency - E Electrode potential - F Faraday constant - i _p Partial current density of step p of reaction scheme - i _t Total current density - k _fp Forward electrochemical rate constant of step p - k _Lj Mass transfer coefficient for species j - K _L Dimensionless mass transfer parameter - n _p Number of electrons in step p of reaction scheme - S Electrode area - t Reaction time - V Batch reactor volume - _p Constant describing potential dependency of reaction rate constant of reaction step p - Y ₁,Y ₂,Y ₃ Effective overall resistance factors - _g Dimensionless reaction time for galvanostatic operation - _p Dimensionless reaction time for potentiostatic operation     

Kinetics of o-Xylene oxidation over sintered vanadium pentoxide in a spinning catalyst basket reactor

Kinetics of vapor phase oxidation of o-xylene has been studied over sintered and compacted vanadium pentoxide in a continuous stirred tank catalytic reactor in the temperature range of 450–517°C at atmospheric pressure. The major product obtained is phthalic anhydride. The other products are maleic anhydride and carbon dioxide. The reaction rate data are well represented (with average absolute deviation less than 6%) by the following expression derived by applying the steady-state oxidation-reduction model of Mars and van Krevelen to a parallel reaction scheme and assuming first order with respect to both o-xylene and oxygen: Significantly, the activation energies for all three postulated reactions with rate constants k₁, k₂, and k₃ turn out to be identical having a value of 14.8 kcal/mole, which may be taken to imply that there is only one rate-influencing reaction step for all the products and not three as assumed in deriving this equation.     

Recycle reactor models for complex electrochemical/chemical reaction systems

The performance of complex electrochemical reaction sequences in recycle plug flow reactors is mathematically modelled. The reactions include successive electron transfers (EE reactions), chemical reaction interposed between successive electron transfers (ECE reactions), simultaneous electron transfers and simultaneous electron transfer and chemical reaction. Both potentiostatic and galvanostatic operations are considered and the effects of important parameters such as mass transport coefficient, recycle ratio and chemical reaction rate in the recycle loop are highlighted. This is done by considering two important electro-organic synthesis reactions, the production ofp-aminophenol and the reduction of oxalic acid to glyoxylic acid.Nomenclature a activity factor - C _ji concentration of species j at reactor inlet - C _j bulk concentration of species j - C _j ^s surface concentration of species j - C _j ^e concentration of component j returned to reactor inlet stream - C _j concentration from reactor outlet - C _je equilibrium concentration - E electrode potential - F Faraday number - i _n partial current density of stepn - i _T total current density - k deactivation rate constant - k _f n forward electrochemical rate constant of stepn - k _b n backward electrochemical rate constant of stepn - k _f forward chemical reaction rate constant - k _r reverse chemical reaction rate constant - k _Lj mass transfer coefficient for species j - k _a forward adsorption rate constant - k _d reverse adsorption rate constant - L reactor length - r recycle ratio - t reaction time - u velocity - Q flow rate - x reactor dimension - _n constant describing potential dependency of reverse reaction rate constant - _n constant describing potential dependency of forward reaction rate constant - _j surface concentration of adsorbed species j - electrode area per unit length - residence time of fluid in recycle loop     

New approach for the estimation of kinetic parameters in emulsion polymerization systems. II. Homopolymerization under conditions where n̄ > 0.5

A new approach for the estimation of kinetic parameters in emulsion polymerization systems in which the average number of radicals per particle exceeds 0.5 is presented. The approach uses the time evolution of the conversion in chemically initiated systems and is based on a model that includes fundamental parameters such as the propagation rate constant, k_p, the termination rate constant in the polymer particles, k_t, the rate coefficient for initiator decomposition, k_I, and the entry, k_a, and exit, k_d, rate coefficients. It was found that k_p, k_t, k_I, k_a, and, under some circumstances, k_d can be accurately estimated provided that termination in the aqueous phase is significant. When the extent of the aqueous phase termination is negligible, only k_p, k_t, and k_I can be estimated. The effect of both the experimental noise level and the run-to-run irreproducibility on the accuracy of the estimates was studied. In addition, it was found that significant inaccuracies resulted from the poor determination of the exact time when polymerization begins. A method to circumvent this problem was proposed.     

Kinetics of the oxidation of carbon monoxide on a supported ferric oxide catalyst

Kinetic studies were made of the oxidation of carbon monoxide to carbon dioxide in a fixed bed of ferric oxide catalyst. It was found that the rate of oxidation, R, is given by the equation R = k¹ k₁pco/1+(k₁/k₂)pco where k¹, k₁ and k₂ are constants and pco is the partial pressure of carbon monoxide. This rate law is similar to that derived for the same reaction on a vanadium oxide catalyst. The rate equation reduces to first order for carbon monoxide concentrations < 1 %.     

Urethanes. I. Organometallic catalysis of the reaction of alcohols with isocyanates

The catalysis of the reaction of n-butyl alcohol with isocyanates, using organometallic derivatives of lead, tin, and mercury, has been investigated. The rate of the reaction was measured by following the disappearance of the isocyanate absorption in the infrared. Phenyl, n-butyl, and cyclohexyl isocyanate were chosen to represent typical aromatic primary and secondary aliphatic isocyanates. Within the same series of catalysts, R_nMOAc, the catalytic effect decreases in the order RHg > R₃Sn > R₃Pb; and in all cases R = aryl > R = alkyl. The electronic effects of substituents on the aryl moiety are not pronounced. Changes in X of R_nMX greatly affect the catalytic activity. The mechanism of organometallic catalysis of the alcohol-isocyanate reaction occurs via a template-type mechanism whereby the catalyst acts to complex both reactants in a catalyst phase allowing the reaction to occur with greater facility.     

Photocatalytic decolorization of Basic Blue 41 using TiO2-Fe3O4-bentonite coating applied to ceramic in continuous system

Abstract

Photocatalytic degradation/decolorization of Basic Blue 41 dye assisted by UV radiation has been studied over TiO₂-Fe₃O₄ supported by bentonite. In this experiment, photocatalytic decolorization process was performed continuously; where dye feed solution was supplied to a coated-ceramic vessel. The influence of the initial concentration, pH, and flow rate of the dye feed solution on the degradation efficiency process was examined in this study. The results showed that the increase in the dye concentration and flow rate reduces decolorization efficiency. The highest decolorization efficiency was at pH of 5.5. The kinetic study of this photo-decolorization indicated that under the experimental condition, the photocatalytic kinetic process followed first-order kinetics on the basis of Langmuir–Hinshelwood heterogeneous reaction mechanism, where the reaction rate constant, namely k_r, is 0.7707 and the adsorption rate constant, namely K, is 0.01298.