The kinetics study of the reduction of Fast Green dye with cetylpyridinum chloride as cationic surfactant

The kinetics of the reaction of Fast Green dye (FG) with cetylpyridinum chloride was studied in alkaline medium by UV-Visible spectrophotometer. Reduction of Fast Green dye was carried out by varying the fast green dye concentration, cetylpyridinum chloride concentration and concentration of sodium hydroxide. In the present study the reduction of dye was carried out in order to reduce the color content. The interaction of dye was carried out with reducing analyte (cetylpyridinum chloride). The rate of the reaction was determined by varying the above parameters at different temperatures. It was observed that the reduction followed pseudo first-order kinetics with respect to dye, surfactant, OH⁻ ion concentration according to the following reaction pathway. The mechanism for the photo bleaching of the dye has been proposed and well confirmed by the data simulation procedure. The activation parameters of the reaction like entropy of activation (ΔS) and free energy of activation (ΔG) showed the extremely solvated states of transient complex which was less disorderly arranged than the oxidized form of dye, whereas E _a values reflects a high amount of energy required for the reduction of dye with cetylpyridinum chloride.     

Reduction Kinetics of Thionine in Aerobic Condition with D-Galactose

Reduction kinetics of thionine (Th) with D-galactose (RH) was observed on a UV/Visible 1601 Shimadzu spectrophotometer at λmax 599 nm. The results showed that the initially slow reduction kinetics got enhanced and proceeded to completion within a few minutes. A pseudo first order kinetics was observed when influence of different parameters like concentration of dye and reductant, ionic strength and temperature was investigated. A significant shift in wave length from 599 to 517 nm was observed at alkaline pH whereas addition of a small amount of acid caused a shift in equilibrium. This resulted in the generation of oxidized form of thionine which was pragmatic in the presence of atmospheric oxygen. Change in ionic strength at elevated temperature lied to decrease in the rate constant. Thermodynamics activation parameters like Ea reflects a high amount of energy required for reduction of Th with RH whereas entropy of activation (∆S!) and free energy of activation (∆G!) show the highly solvated states of transient complex which was less disorderly arranged than the oxidized form of dye. A mechanism consistent with above findings has been discussed in the relevant section of paper.     

Kinetics and mechanism of anation of cis -diaquo- bis -oxalatochromate(III) ion byDL -alanine in ethanol-water mixtures of varying dielectric constant

The kinetics of the anation reaction of cis-diaquo-bis-oxalatochromate(III) ion by DL-alanine has been studied spectrophotometrically in the pH range 3.8 to 7.3, where DL-alanine remains in zwitterionic form. A second-order rate law has been established. Reaction rates in three different ethanol-water mixtures were measured. In each solvent medium the anation rate is higher as compared to water exchange reaction at a particular temperature. The activation parameters (gDH^# and ΔS^#) in different ethanol-water mixtures were obtained from Eyring plots. ΔG^#(ΔH^# −TΔS ^#) values were calculated in each solvent medium and compared with that of the isotopic water exchange process. A reaction mechanism involving theS _N2 path has been suggested.     

Thermokinetic Research Method for Bacterial Growth in Conduction Calorimeter

This paper presents the basic equations of thermokinetics and the thermoanalytical curve equation for bacterial growth in conduction calorimeter on the basis of the basic theory of thermokinetics. The bacterial growths in the log phase for Vibro metschnikovii and Bacillus subtilis at different temperatures were calorimetrically investigated. The rate constant of bacterial growth, the cooling constant of the thermokinetic system, the generation time and the pre-exponential factor at different temperature were obtained, which allowed to evaluate the activation energy of bacterial growth (E _a). According to the transition-state theory of chemical kinetics, the activation enthalpy (ΔS ^≠), the activation Gibbs free energy (ΔG ^≠) and equilibrium constant (K ^≠) of the activated state at different temperatures were also obtained. The above results showed that the research method suggested in this paper was reasonable. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kinetics and thermodynamics of the electrodeposition of palladium, thallium, and tellurium from different baths

Some kinetic and activation thermodynamic functions for the electrodeposition of palladium, thallium, and tellurium from the best selected baths, viz. niclosamide bath [5-chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxybenzamide] for Pd, alizarin red bath for Tl, and salicylaldehyde bath for Te, are determined. Reaction rate constant (k), half-lifetime (t _1/2), activation energy (E _a), and such activation thermodynamic parameters as entropy change (ΔS*), enthalpy change (ΔH*), and Gibbs free energy (ΔG*) are calculated by applying the rate theory of the first-order reaction and the Eyring theory of the reaction rate. The effect of temperature change in the range of 30–60°C on the above parameters is studied and thoroughly discussed. The effect of metal type on both the reaction rate and the activation energy is also investigated. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 3, pp. 264–271. The text was submitted by the authors in English.     

Oxidation of 1,3,7-trimethylxanthine by hypochlorite ion

The kinetics of the oxidative conversion of 1,3,7-trimethylxanthine upon treatment with hypochlorite ions (OCl⁻) in aqueous medium at 283–298 K and pH 8.2 was studied. The reaction order with respect to each component was determined and proved to be 1. It was established that the temperature dependence of the reaction rate follows the Arrhenius equation. The activation parameters of the reaction were measured: E _a = 33.58 kJ/mol, ΔH ^≠ = 31.12 kJ/mol, ΔS ^≠ = −170.02 J/(K mol), ΔG ^≠ = 81.45 kJ/mol. The stoichiometry of the reaction was studied, and the chemistry of the oxidative conversion of caffeine treated with OCl⁻ is discussed.     

Studies on temperature dependent kinetics of <Emphasis Type="Italic">Aspergillus awamori</Emphasis> feruloyl esterase in water solutions

The initial reaction rate (V ₀) for the esterification reaction of feruloyl esterase (FAE-II) at different temperatures (288, 298, 308, 318, 328, 338, 348, and 358 K) and various ethyl ferulate concentrations [(2, 4, 6, 8, 10, 12, 14, and 16) × 10⁻⁴ mol l⁻¹ of ethyl ferulate in water] were determined. The Lineweaver-Burk double reciprocal plot yielded the kinetic parameters (maximal velocity V _max, Michaelis constant K _m, and second order rate constant V/K). The effects of temperature on those 3 kinetic parameters were presented and discussed. The thermodynamic parameters ΔH* (enthalpy of activation), ΔG* (free energy of activation), ΔS* (entropy of activation), ΔG _E-S (free energy change of substrate binding), ΔG _E-T (free energy change of transition state formation), related to that biochemical process were determined and discussed from van’t Hoff plot, Arrhenius plot, and Eyring plot.     

Synthesis,spectroscopic characterization,thermal, and photostability studies of 2-(2′-hydroxy-5′-phenyl)-5-aminobenzotriazole complexes

Three Mn(II), Co(II), and Cu(II) new transition metal complexes of the fluorescence dye: 2-(2′-hydroxy-5′-phenyl)-5-aminobenzotriazole/PBT derived from o-aminophenol and m-phenylenediamine have been synthesized. The structural interpretations were confirmed from elemental analyses, magnetic susceptibility and molar conductivity, as well as from mass, IR, UV–Vis spectral studies. From the analytical, spectroscopic, and thermal data, the stoichiometry of the mentioned complexes was found to be 1:2 (metal:ligand). The molar conductance data revealed that all the metal chelates are non-electrolytes and the chloride ions exist inside the coordination sphere. The thermal stabilities of these complexes were studied by thermogravimetric (TG/DTG) and the decomposition steps of these three complexes are investigated. The kinetic parameters such as the energy of activation (E*), pre-exponential factor (A), activation entropy (ΔS*), activation enthalpy (ΔH*), and free energy of activation (ΔG*) have been reported. Photostability of phenyl benzotriazole as fluorescence dye and their metal complexes doped in polymethyl methacrylate/PMMA were exposed to UV–Vis radiation and the change in the absorption spectra was achieved at different times during irradiation period.     

Production of low sulfur diesel fuel via adsorption: an equilibrium and kinetic study on the adsorption of dibenzothiophene onto NaY zeolite

The adsorption of dibenzothiophene (DBT) in hexadecane onto NaY zeolite has been studied by performing equilibrium and kinetic adsorption experiments. The influence of several variables such as contact time, initial concentration of DBT and temperature on the adsorption has been investigated. The results show that the isothermal equilibrium can be represented by the Langmuir equation. The maximum adsorption capacity at different temperatures and the corresponding Langmuir constant (K _L ) have been deduced. The thermodynamic parameters (ΔG ⁰,ΔH ⁰,ΔS ⁰) for the adsorption of DBT have also been calculated from the temperature dependence of K _L using the van’t Hoff equation. The value of ΔH ⁰,ΔS ⁰ are found to be −30.3 kJ mol⁻¹ and −33.2 J mol⁻¹ K⁻¹ respectively. The adsorption is spontaneous and exothermic. The kinetics for the adsorption process can be described by either the Langmuir model or a pseudo-second-order model. It is found that the adsorption capacity and the initial rate of adsorption are dependent on contact time, temperature and the initial DBT concentration. The low apparent activation energy (12.4 kJ mol⁻¹) indicates that adsorption has a low potential barrier suggesting a mass transfer controlled process. In addition, the competitive adsorption between DBT, naphthalene and quinoline on NaY was also investigated.     

Adsorption study of an industrial dye by an organic clay

In this study, the adsorption of an industrial dye Supranol Yellow 4GL onto Cetyltrimethylammonium-bentonite (CTAB-bentonite) is investigated. The organobentonite is synthesised by exchanging cetyltrimethylammonium cations (CTAB) with inorganic ions on the surface of bentonite. The adsorption of Supranol Yellow 4GL onto organobentonite is found to be maximum when the concentration of CTAB exchanged is 100% according to the cation exchange capacity of the clay (CEC). The modification of organobentonite is examined using XRD and FTIR techniques. The effect of the process parameters such as: contact time, adsorbate concentration, adsorbent dose, pH and temperature are reported. Nearly 1200 seconds of contact time are found to be sufficient for the adsorption to reach equilibrium. The pseudo second order model is used to describe the kinetic data, and the rate constant is therefore evaluated. The dye adsorption to organobentonite is characterized by monolayer isotherm and caused by adsorption with relatively strong uptake. The Langmuir and Freundlich models adsorption are applied to describe the isotherm equilibrium and to determine its constants. The Langmuir and Freundlich models agree well with the experimental data with a adsorption capacity of 0.5 g of dye per g of organobentonite. A better fixation was obtained at acidic pH. The effect of temperature on the adsorption of dye has been also studied and the thermodynamic parameters ΔH, ΔS, ΔG, were determined. Organobentonite is found to be effective for removing Supranol Yellow 4GL dye from wastewater.     

Reduction of water-soluble colloidal manganese dioxide by thiourea: a kinetic and mechanistic study

Kinetic data for the colloidal MnO₂–thiourea redox system are reported for the first time. The reduction of water-soluble colloidal MnO₂ by thiourea (sulfur containing reductant) in aqueous perchloric acid medium has shown that it proceeds in two stages, i.e., a fast stage followed by a relatively slow second stage. The log (absorbance) versus time plot deviates from linearity. The kinetics of both the stages was investigated spectrophotometrically. The first-order kinetics with respect to [thiourea] at low concentration shifts to zero-order at higher concentration. The reaction rate increases with [HClO₄] and the kinetics reveals complex order dependence in [HClO₄]. Addition of P₂O ₇ ⁴⁻ and F⁻ in the form of Na₄P₂O₇ and NaF, respectively, has inhibitory effect on the reaction rate. The reaction proceeds through the fast adsorption of thiourea on the surface of the colloidal MnO₂. A mechanism involving the protonated thiourea as the reactive reductant species is proposed. The observed results are discussed in terms of Michaelis–Menten/Langmuir–Hinshelwood model. From the observed kinetic data, colloidal MnO₂–thiourea adsorption constant (K _ad1) and rate constant (k ₁) were calculated to be 1.25×10¹⁰ mol⁻¹ dm³ and 3.1×10⁻⁴ s⁻¹, respectively. The variation of temperature does not have any effect on the reaction rate.     

Joint effect of structure and temperature on the rates of the reactions of 3,5-dinitrophenyloxirane with arenesulfonic acids: Compensation effect and isoparametricity

The joint effect of structure and temperature on the rate and free energy of activation of the reactions of 3,5-dinitrophenyloxirane with arenesulfonic acids YC₆H₄SO₃H in a dioxane-diglyme (1: 1 vol/vol) mixture is reported. A correlation analysis of the results of a multifactor kinetic experiment has demonstrated the nonadditivity (interaction) of the effects of the substituent Y and temperature for a cross reaction series. The pronounced kinetic enthalpy-entropy compensation effect provided experimental evidence for the isoparametricity phenomenon: at the isoparametric temperature point (isokinetic temperature), the rate of the reaction is independent of the structure of Y. At the isoparametric point for the constant of the substituent Y, the free energy of activation is temperature-independent and the entropy of activation is ΔS ^≠ = 0. On passing through this point, ΔS ^≠ changes its sign. The isoparametric points for the parameters of the varied factors are used in the interpretation of the mechanism of oxirane ring opening.     

Adsorption of reactive brilliant red K-2BP on activated carbon developed from sewage sludge

Activated carbon was prepared from the sewage sludge of municipal wastewater treatment plant by chemical activation (activation reagent is ZnCl₂) and was used for the adsorption of dye (reactive brilliant red K-2BP). The impact of adsorbent amount, adsorption time and pH value on adsorption effect, the adsorption kinetics, and the adsorption thermodynamics were discussed according to batch adsorption tests. The results indicated that the activated carbon developed from sewage sludge (ACSS), which was mesoporous, possessed opened porous structures. The iodine number of the ACSS was 326 mg·g⁻¹. The rate of achievement was 51.31%. The BET surface area was 298 m²·g⁻¹ and the contents of heavy metals in the leachate didn’t exceed the contents limit. The adsorption kinetics of reactive brilliant red K-2BP on the ACSS was accorded with the two-step kinetics rate equation and pseudo-second-order kinetics equation. Compared to the Freundlich isotherm equation, the Langmuir isotherm equation showed better applicability for the adsorption. The adsorption which was favorable was an endothermic (enthalpy ΔH > 0) and spontaneous (free energy ΔG < 0) process and was accompanied by an increase in entropy (ΔS > 0). __________ Translated from Journal of Shandong University (Natural Science), 2007, 42(3): 64–70 [译自: 山东大学学报(理学版)]     

Influence of solvent structure on the aquation of <Emphasis Type="BoldItalic">trans</Emphasis>-[Ru(3-MePy)<Subscript>4</Subscript>Cl<Subscript>2</Subscript>] complex in mixed aqueous solvents

The kinetics of the solvolytic aquation of trans-[Ru (3-Me Py)₄Cl₂] was studied spectrophotometrically in water – isopropanol in the range (30–90% v/v), and water acetonitrile in the range (10–70% v/v), and in the temperature range 50–65 °C. Plots of log k versus the reciprocal of the relative permittivity and Grunwald–Winstien gave non-linear plots. This non-linearity is derived from a large differential effect of solvent structure between the initial and transition states. The plot of log k versus water concentration was also non linear; evidence for the presence of a S _N ¹ mechanism. However, extrema in the variation of enthalpy ΔH* and entropy ΔS* of activation correlate well with the extrema in physical properties of the mixtures which are related to changes in solvent structure. Linear plots of ΔH* versus ΔS* were obtained and the iso- kinetic temperature indicates that the reaction is entropy controlled.     

Removal of reactive dye brilliant red HE-3B from aqueous solutions by hydrolyzed polyacrylonitrile fibres: equilibrium and kinetics modelling

A cheap and efficient fibrous hydrolyzed polyacrylonitrile (HPAN) sorbent was obtained by alkaline hydrolysis of Romanian polyacrylonitrile fibres. Scanning electronic microscopy and infrared spectroscopy were used to characterize the hydrolyzed product and to confirm its functionalization. The adsorptive potential of the proposed sorbent for reactive dye Brilliant Red HE-3B removal from aqueous solutions of pH=2 was examined by the batch technique as a function of dye concentration, temperature solution and contact time. The Freundlich, Langmuir and Dubinin-Radushkevich adsorption models were applied to describe equilibrium sorption data and to determine the corresponding isotherm constants. The thermodynamic parameters ΔG, ΔH and ΔS were also determined; the values obtained show that sorption of reactive dye on HPAN fibres is a spontaneous, endothermic and entropy-driven process. The kinetics of sorption of the reactive dye were analyzed using pseudo-first order and pseudo-second order kinetic models. The kinetic data fitted well to pseudo-second order kinetics, indicating the chemisorption of reactive dye onto the fibrous sorbent. The sorption mechanism of the dye onto hydrolyzed fibres was confirmed by FTIR spectroscopy. The dye-loaded HPAN sorbent can be regenerated by treatment with 0.1M NaOH and the regenerated sorbent may be reused in several adsorption-desorption cycles. The results of this study provided evidence that the HPAN fibres are effective for removing reactive dye Brilliant Red HE-3B from aqueous effluents.      

Studies on Cobalt(III) Metallosurfactants. Kinetics and Mechanism of Reduction of Cobalt(III) by Iron(II) in Aqueous Acid Medium

The kinetics and mechanism of reduction of the surfactant complex ions, cis-chloro/bromo(dodecylamine)(triethylenetetramine)cobalt(III) by iron(II) in aqueous solution were studied at 303, 308 and 313 K by spectrophotometry under pseudo-first-order conditions using an excess of the reductant. The second-order rate constant increases with cobalt(III) concentration and the presence of aggregation of the complex itself alters the reaction rate. The reductions are acid-independent in the range [H⁺] = 0.05–0.25 mol dm⁻³. Variation of ionic strength (μ) influences the reaction rate. Activation and thermodynamic parameters have been computed. It is suggested that the reaction of Fe²⁺(aq) with the cobalt(III) complex proceeds by an inner-sphere mechanism. The critical micelle concentration (CMC) values of these surfactant metal complexes in aqueous solution were obtained from conductance measurements. Specific conductivity data (at 303, 308 and 313 K) served for the evaluation of the temperature-dependent CMC and the standard Gibbs energy of micellization (ΔG_m⁰).     

Adsorption of methylene blue dye from aqueous solution by agricultural waste: Equilibrium,thermodynamics, kinetics,mechanism and process design

The adsorption of methylene blue (MB) dye from aqueous solution onto a cashew nut shell (CNS) was investigated as a function of parameters such as solution pH, CNS dose, contact time, initial MB dye concentration and temperature. The CNS was shown to be effective for the quantitative removal of MB dye, and the equilibrium was reached in 60 min. The experimental data were analysed by two-parameter isotherms (Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models) using nonlinear regression analysis. The characteristic parameters for each isotherm and the related correlation coefficients were determined. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were also evaluated, the sorption process was found to be spontaneous and exothermic. Pseudo-first-order, pseudo-second-order and Elovich kinetic models were used to analyze the adsorption process. The results of the kinetic study suggest that the adsorption of MB dye matches the pseudo-second-order equation, suggesting that the adsorption process is presumably chemisorption. The adsorption process was found to be controlled by both surface and pore diffusion. Analysis of adsorption data using a Boyd kinetic plot confirmed that the external mass transfer is a rate determining step in the sorption process. A single-stage batch adsorber was designed for different CNS doses to effluent volume ratios using the Freundlich equation. The results indicated that the CNS could be used effectively to adsorb MB dye from aqueous solutions.     

Cure kinetics of thermosetting bisphenol E cyanate ester

Resin injection repair is a common method to repair delamination damage in polymer matrix composites (PMCs). To repair high-temperature PMCs, the resin should have a very low viscosity, yet cure into a compatible adhesive with high temperature stability. Normally, thermosetting polymers with high glass transition temperatures (T _g) are made from monomers with high room temperature viscosities. Among the high temperature resins, bisphenol E cyanate ester (BECy, 1,1’-bis(4-cyanatophenyl)ethane), is unique because it has an extremely low viscosity of 0.09–0.12 Pa s at room temperature yet polymerizes as a cross-linked thermoset with a high T _g of 274°C. BECy monomer is cured via a trimerization reaction, without volatile products, to form the high T _g amorphous network. In this study, the cure kinetics of BECy is investigated by differential scanning calorimetry (DSC). Both dynamic and isothermal experiments were carried out to obtain the kinetic parameters. An autocatalytic model was successfully used to model isothermal curing. The activation energy from the autocatalytic model is 60.3 kJ mol⁻¹ and the total reaction order is about 2.4. The empirical DiBenedetto equation was used to evaluate the relationship between T _g and conversion. The activation energy of BECy from the dynamic experiments is 66.7 kJ mol⁻¹ based on Kissinger’s method, while isoconversional analysis shows the activation energy changes as the reaction progresses.     

Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

The oxidation kinetics of crystal violet (a triphenylmethane dye) by potassium permanganate was focused in an acidic medium by the spectrophotometric method at 584 nm. The oxidation reaction of crystal violet by potassium permanganate is carried out in an acidic medium at different temperatures ranging within 298–318 K. The kinetic study was carried out to investigate the effect of the concentration, ionic strength and temperature. The reaction followed first order kinetics with respect to potassium permanganate and crystal violet and the overall rate of the reaction was found to be second order. Thermodynamic activation parameters like the activation energy (E_a), enthalpy change (ΔH*), free energy change (ΔG*), and entropy change (ΔS*) have also been evaluated.     

Thermochemistry of europium and dithiocarbamate complex Eu(C5H8NS2)3(C12H8N2)

A solid complex Eu(C₅H₈NS₂)₃(C₁₂H₈N₂) has been obtained from reaction of hydrous europium chloride with ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen⋅H₂O) in absolute ethanol. IR spectrum of the complex indicated that Eu³⁺ in the complex coordinated with sulfur atoms from the APDC and nitrogen atoms from the o-phen. TG-DTG investigation provided the evidence that the title complex was decomposed into EuS. The enthalpy change of the reaction of formation of the complex in ethanol, Δ_r H _m ^θ(l), as –22.214±0.081 kJ mol^–1, and the molar heat capacity of the complex, c _m, as 61.676±0.651 J mol^–1 K^–1, at 298.15 K were determined by an RD-496 III type microcalorimeter. The enthalpy change of the reaction of formation of the complex in solid, Δ_r H _m ^θ(s), was calculated as 54.527±0.314 kJ mol^–1 through a thermochemistry cycle. Based on the thermodynamics and kinetics on the reaction of formation of the complex in ethanol at different temperatures, fundamental parameters, including the activation enthalpy (ΔH _≠ ^θ), the activation entropy (ΔS _≠ ^θ), the activation free energy (ΔG _≠ ^θ), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained. The constant-volume combustion energy of the complex, Δ_c U, was determined as –16937.88±9.79 kJ mol^–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δ_c H _m ^θ, and standard enthalpy of formation, Δ_f H _m ^θ, were calculated to be –16953.37±9.79 and –1708.23±10.69 kJ mol^–1, respectively.