Semi-empirical Kinetics Research Articles

Continuous Synthesis of 5-Oxohexanenitrile in a Microreactor: From Kinetic Study to Reactor Modeling

Synthesis experiments of 5-oxohexanenitrile through the addition of acetone to acrylonitrile at the temperature range of 200–230 °C were carried out in a microreactor. Based on the experimental data, a semiempirical kinetic model was established and validated. According to the developed kinetic model, the effects of the molar ratio of acetone to acrylonitrile, the concentration of N-propylamine, and the initial water content were further investigated. By coupling the semiempirical kinetics with the plug flow reactor model, studies on the effect of the reactor diameter, the residence time, and the reaction temperature were performed to shed some light on the design and optimization of the industrial tubular reactors for the production of 5-oxohexanenitrile.

Fluoride Leaching of Titanium from Ti-Bearing Electric Furnace Slag in [NH4+]-[F−] Solution

The effects of F− concentration, leaching temperature, and time on the Ti leaching from Ti-bearing electric furnace slag (TEFS) by [NH4+]-[F−] solution leaching process was investigated to reveal the leaching mechanism and kinetics of titanium. The results indicated that the Ti leaching rate obviously increased with the increase of leaching temperature and F− concentration. The kinetic equation of Ti leaching was obtained, and the activation energy was 52.30 kJ/mol. The fitting results of kinetic equations and calculated values of activation energy both indicated that the leaching rate of TEFS was controlled by surface chemical reaction. The semi-empirical kinetics equation was consistent with the real experimental results, with a correlation coefficient (R2) of 0.996. The Ti leaching rate reached 92.83% after leaching at 90 °C for 20 min with F− concentration of 14 mol/L and [NH4+]/[F−] ratio of 0.4. The leaching rates of Si, Fe, V, Mn, and Cr were 94.03%, 7.24%, 5.36%, 4.54%, and 1.73%, respectively. The Ca, Mg, and Al elements were converted to (NH4)3AlF6 and CaMg2Al2F12 in the residue, which can transform into stable oxides and fluorides after pyro-hydrolyzing and calcinating.

Homogeneous synthesis of hydroxylamine hydrochloride via acid-catalyzed hydrolysis of nitromethane

A continuous homogeneous synthesis of NH2OH·HCl was achieved and well described with a segmented semi-empirical kinetics model.

Kinetics and Mechanism of Counterionic Salt-Catalysed Piperidinolysis of Anionic Phenyl Salicylate in the Presence of Cationic–Nonionic Mixed Micelles

The quantitative correlation of counterion-affinity to aqueous hexadecyltrimethylammonium bromide (HDAB, cationic micelles/nanoparticles) and the counterion-induced HDAB micellar growth, in the presence of different amounts of poly(ethylene glycol hexadecyl ether) (C16E20, nonionic surfactant), was achieved by the use of a semi-empirical kinetic (SEK) method. The values of the ratio of cationic HDAB, as well as mixed HDAB–C16E20, micellar binding constants of X and Br, KX/ KBr (= KXBr or RXBr) for X = 4-ClC6H4CO2-, were obtained by the SEK method. The concentration range (0.006–0.015 M) of pure HDAB was found to have no influence on the values of KXBr or RXBr. These observations were also recorded upon addition of a nonionic surfactant, C16E20, in an aqueous solution of HDAB. The mean value of KXBr or RXBr obtained in the presence of pure HDAB ( KXBr or RXBr = 50.3) is 2.3 times larger than that in the presence of mixed HDAB–C16E20 (m KXBr or m RXBr = 21.7). From rheometric measurements of aqueous HDA+/4-ClC6H4CO2- with 0.015 M HDAB, single symmetric maxima (at both 25 and 35 °C) were obtained at [4-ClC6H4CO2Na] = 0.03 M. This is evidence for the existence of wormlike micelles/nanoparticles. However, the absence of a maximum in rheometric data for aqueous HDA+/C16E20/4-ClC6H4CO2- with 0.015 M HDAB and 0.006 M C16E20 at various [4-ClC6H4CO2Na] revealed the existence of spherical micelles.

Study of Cationic and Nonionic Mixed Micelles with NaBr and 3,5-Cl2C6H3CO2Na by Use of Probe Nucleophilic Reaction of Piperidine with Ionized Phenyl Salicylate.

Behaviors of cationic and nonionic mixed micelles in the form of hexadecyltrimethylammonium bromide (HDABr) and hexadecyltrimethylammonium bromide-Polyethylene glycol hexadecyl ether (C16E20), in the presence of inert salts (NaBr and 3,5-dichlorosodium benzoate), by the use of reaction probe between Pp and ionized PhSH (Pp = piperidine and PhSH = phenyl salicylate), has been reported in this work. The values of RXBr (RXBr denotes ion exchange constants obtained in the presence of micelles of different structural features) or KXBr (KXBr denotes ion exchange constants obtained in the presence of micelles of the same structural features) for 3,5-Cl2C6H3CO2- were almost the same at three different [HDABr]T (0.006, 0.010 and 0.015 M). The average value of RXBr or KXBr determined, in the presence of pure HDABr micelles, using semi empirical kinetic (SEK) method appeared to be almost 2½-fold larger (RXBr or KXBr = 198) than that in the presence of mixed HDABr-C16E20 micelles (RXBr or KXBr = 78). Rheological measurements indicated the existence of wormlike/twisted micelles and vesicle at 0.015 M pure HDABr, various [3,5-Cl2C6H3CO2Na], and 25 and 35℃ whereas there were evidence of only spherical micelles in the presence of mixed HDABr-C16E20 ([HDABr]T = 0.015 M and [C16E20]T = 0.006 M) at both temperatures.

Preparation of bismuth subcarbonate by liquid ball-milling transformation method from bismuth oxide

In order to solve the problems of environment pollution and high cost in traditional process of bismuth subcarbonate preparation, a new process using ball-milling transformation method from NH4HCO3 and Bi2O3 was proposed. Additionally, the kinetics of bismuth subcarbonate preparation was studied. Effects of reaction temperature, particle size of bismuth oxide, solid-to-liquid ratio and concentrations of ammonium bicarbonate on the conversion rate of bismuth oxide were studied. The results indicate that the conversion rate of bismuth oxide significantly increased under the conditions of higher temperature, smaller particle size, higher concentration of ammonium bicarbonate and smaller solid-to-liquid ratio. The XRD and ICP-AES analyses show that the purity of product is high. The reaction kinetics with activation energy of 9.783 kJ/mol was analyzed by shrinking core model, and the whole transformation process is controlled by solid product layer diffusion. A semi-empirical kinetics equation was obtained to describe the conversion process.

Quantitative correlation between counterion (X) binding affinity to cationic micelles and X – Induced micellar growth for substituted iodobenzoates (X)

A new semi-empirical kinetic (SEK) method has been used to calculate the values of KXBr or RXBr (X represents substituted iodobenzoates), with KX and KBr representing CTABr micellar binding constants of counterions X− (in the presence of either spherical or non-spherical micelles) and Br− (in the presence of only spherical micelles), respectively. Steady-shear rheological properties of mixed 0.015M CTABr/[MX] aqueous solutions reveal the presence of flexible wormlike micelles where MX represents sodium 3- and 4-iodobenzoates. The maxima of the plots of viscosity vs. [MX] at 0.015M CTABr for MX representing sodium 3- and 4-iodobenzoates support the presence of long linear and entangled wormlike micelles.

Quantitative Correlation between Counterion (X) Affinity to Cationic Micelles and X-Induced Micellar Growth for X = 2,4-; 2,5-; 2,6- and 3,4-Dichlorobenzoate Ions

A semi empirical kinetic (SEK) method has been used to determine the ratio of cetyltrimethylammonium bromide (CTABr) micellar binding constants of counterion X⁻ and Br⁻ (a reference counterion), i.e. K(X)/K(Br) (=R(X)(Br)). The values of K(X) and K(Br) have been derived from the kinetic parameters obtained in the presence spherical/non-spherical and spherical micelles, respectively. This rather new method gives the respective mean values of R(X)(Br) as 45±2, 25±3, 4.7±0.6 and 119±10 for X=2,4-, 2,5-, 2,6- and 3,4-Cl₂C₆H₃CO₂⁻ (Cl₂Bz'Na). Literature lacks the report on the values of R(X)(Br) for all X except for X=2,6-Cl₂C₆H₃CO₂⁻ (2,6-Cl2Bz'⁻) for which the reported value is 5.0. Rheological properties, such as shear thinning behavior, reveal indirectly the presence of wormlike micelles (WM) in the CTABr micellar solutions containing MX for all X except X=2,6-Cl₂Bz'⁻. The micelles remain spherical within [2,6-Cl₂Bz'⁻] range 0.01-0.34 M at 0.015 M CTABr. The maxima of the plots of zero shear viscosity, η₀, (obtained from the initial plateau region of flow curves, i.e. η vs. γ curve) vs. [MX] (MX=2,4-, 2,5- and 3,4-Cl₂Bz'Na) at 0.015 M CTABr also support indirectly the presence of linear, entangled and branched WM.

A Semi-Empirical Spectrophotometric (SESp) Method for the Indirect Determination of the Ratio of Cationic Micellar Binding Constants of Counterions X^|^ndash; and Br^|^ndash; (KX/KBr)

The semi-empirical spectrophotometric (SESp) method, for the indirect determination of ion exchange constants (K(X)(Br)) of ion exchange processes occurring between counterions (X⁻ and Br⁻) at the cationic micellar surface, is described in this article. The method uses an anionic spectrophotometric probe molecule, N-(2-methoxyphenyl)phthalamate ion (1⁻), which measures the effects of varying concentrations of inert inorganic or organic salt (Na(v)X, v = 1, 2) on absorbance, (A(ob)) at 310 nm, of samples containing constant concentrations of 1⁻, NaOH and cationic micelles. The observed data fit satisfactorily to an empirical equation which gives the values of two empirical constants. These empirical constants lead to the determination of K(X)(Br) (= K(X)/K(Br) with K(X) and K(Br) representing cationic micellar binding constants of counterions X and Br⁻). This method gives values of K(X)(Br) for both moderately hydrophobic and hydrophilic X⁻. The values of K(X)(Br), obtained by using this method, are comparable with the corresponding values of K(X)(Br), obtained by the use of semi-empirical kinetic (SEK) method, for different moderately hydrophobic X. The values of K(X)(Br) for X = Cl⁻ and 2,6-Cl₂C6H₃CO₂⁻, obtained by the use of SESp and SEK methods, are similar to those obtained by the use of other different conventional methods.

Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Airborne particles affect human health and significantly influence visibility and climate. A major fraction of these particles result from the reactions of gaseous precursors to generate low-volatility products such as sulfuric acid and high-molecular weight organics that nucleate to form new particles. Ammonia and, more recently, amines, both of which are ubiquitous in the environment, have also been recognized as important contributors. However, accurately predicting new particle formation in both laboratory systems and in air has been problematic. During the oxidation of organosulfur compounds, gas-phase methanesulfonic acid is formed simultaneously with sulfuric acid, and both are found in particles in coastal regions as well as inland. We show here that: (i) Amines form particles on reaction with methanesulfonic acid, (ii) water vapor is required, and (iii) particle formation can be quantitatively reproduced by a semiempirical kinetics model supported by insights from quantum chemical calculations of likely intermediate clusters. Such an approach may be more broadly applicable in models of outdoor, indoor, and industrial settings where particles are formed, and where accurate modeling is essential for predicting their impact on health, visibility, and climate.