The reaction of Cl with CH(4): a connection between kinetics and dynamics

This paper presents an analysis of the reaction of Cl with CH(4) by combining measurements of thermal rate constants and state-dependent reaction cross sections. State-dependent measurements have shown that the reaction probability is enhanced by vibrational excitation of CH(4). Measured thermal rate constants were fit with a model incorporating this information. The results provide estimates of rate constants at extreme temperatures and information about the temperature and collision energy dependence of the vibrational enhancement.     

Wastewater treatment using photo-impinging streams cyclone reactor: Computational fluid dynamics and kinetics modeling

A photo impinging streams cyclone reactor has been used as a novel apparatus in photocatalytic degradation of organic compounds using titanium dioxide nanoparticles in wastewater. The operating parameters, including catalyst loading, pH, initial phenol concentration and light intensity have been optimized to increase the efficiency of the photocatalytic degradation process within this photoreactor. The results have demonstrated a higher efficiency and an increased performance capability of the present reactor in comparison with the conventional processes. In the next step, residence time distribution (RTD) of the slurry phase within the reactor was measured using the impulse tracer method. A CFD-based model for predicting the RTD was also developed which compared well with the experimental results. The RTD data was finally applied in conjunction with the phenol degradation kinetic model to predict the apparent rate coefficient for such a reaction.     

Fabrication of low surface free energy automotive clear coats: Mechanical and surface chemistry studies

This work aims at improving the surface chemistry and the mechanical properties of a commercial acrylic–melamine clear coat using a functional siliconized additive. The resistance of films against biological degradation was then investigated using pancreatin (simulated bird droppings) and Arabic gum (simulated tree gum). Variations in the surface and bulk chemical structures, as well as the thermomechanical characteristics of the clear coats at different concentrations of the additive, were investigated by a wide range of techniques inclusive of contact angle measurement, gonio‐spectrophotometery, dynamic mechanical thermal analysis (DMTA), energy‐dispersive spectroscopy, atomic force microscope, optical microscope, and attenuated totalreflectance Fourier transform infrared (ATR‐FTIR) spectroscopy. Negligible effect of additive on color change was revealed. It was shown that even at low loadings of additive it could migrate to the surface, producing hydrophobic films with very low surface free energies with water contact angle exceeding 100°. In addition, it was found by DMTA and ATR‐FTIR studies that the functional additive was covalently attached to the acrylic–melamine chains through its hydroxyl groups. However, phase separation was observed at high concentrations of additive, leading to reduced crosslinking density. The clear coat resistance against pancreatin and Arabic gum was improved using optimum concentrations of the additive. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Can isotopic transient and formal steady-state kinetics lead to a converging surface chemistry analysis? Case study on the selective reduction of NO by CH4 over Co-ZSM-5 catalysts

The surface coverage analysis derived from two formal steady-state kinetic models is compared to values directly obtained from steady-state isotopic transient analysis (SSITKA) for the selective catalytic reduction (SCR) of NO by CH₄ over Co-ZSM-5 catalysts. It is shown that the most abundant reacting intermediates are NO _x adspecies, though no clear differentiation between the various adspecies identified by DRIFT spectroscopy was achieved. Less numerous carbon containing adspecies were identified and quantified in the reacting system, essentially as methoxy species. Nitromethane-like intermediates remained undetectable due to a very rapid transformation into N₂ and CO₂. On the basis of these converging kinetic analyses related to each elementary step of the SCR process, a microkinetic model can be derived, which allows describing transient operation, in view of a non steady-state application.     

Effect of pigmentation on the surface chemistry and surface free energy of paper coating binders

The effect of the addition of clay and TiO₂ pigments on the surface energy and surface chemistry of films made from polymers used in paper coating formulations was evaluated. The polymers were carboxymethyl cellulose, polyvinyl alcohol and a protein-based polymer - all water-soluble - and two styrene-butadiene latexes of different carboxylation levels. The morphology of the surfaces was characterized by SEM examination, gloss measurement and stylus profilometry. Chemical composition was determined by EDS and XPS techniques. Surface energy and its Lifshitz-van der Waals and acid-base components were obtained from contact angle measurements using the van Oss et al. approach. Even though the addition of pigment increasingly upset the planar surface of the films, their surface chemistry and surface energy were only slightly affected over the pigmentation range studied (up to 40% by volume) and were dominated by the characteristics of the binder polymer.     

Effect of sintering on surface chemistry and surface energy of pigmented latex coatings

Drying in the absence of water (sintering) of pigmented coatings made of styrene–butadiene (SB) latex and kaolin clay at different levels of pigmentation was investigated. As found from X-ray photoelectron spectroscopy, sintered coatings showed a higher SB area percent on the surface than did latex with a high glass-transition temperature (T_g) and dried at room temperature. This was a result of latex spreading at the surface. Sintering the high-T_g coatings that were dried at room temperature caused a decrease in the surface energy. Drying in the presence of water (wet coalescing) was compared to drying in the absence of water (sintering). Even though sintered coatings were more porous and had higher gloss, no significant difference was found in the SB/clay ratio at the surface or in the surface energy above the critical pigment volume concentration (CPVC). However, at and below CPVC, the sintering process yielded a higher SB content at the surface and a lower surface energy than the wet-coalescing process. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 968–975, 2001     

Relationship between surface chemistry and surface energy of different shape pigment blend coatings

The influence of pigment shapes and pigment blends on the surface energy was investigated and compared with the surface chemistry of pigmented latex coatings. The coatings were made of different volume ratios of two pigments: plate-like kaolin clay pigment and prismatic precipitated calcium carbonate (PCC) pigment. These were mixed together with carboxylated styrene–butadiene–acrylonitrile latex (SBA), and applied over nonabsorbent substrates as well as absorbent substrates. The composition of the surface of the coatings was investigated by X-ray photoelectron spectroscopy (XPS). Two approaches were used to estimate the total surface energy and the components of the coatings: a conventional approach—“the Kaelble approach”—and a more modern approach—“the van Oss approach.” Pigment blends with different shapes and increments caused a change in the surface chemistry and the surface energy of the latex coatings. As the prismatic PCC pigment particles increased in the kaolin/SBA coating system, the SBA latex content at the coating surface increased and the total surface energy of the coating decreased. This is valid for both nonabsorbent as well as absorbent substrates. It was found that there was a strong correlation between the surface energy and the surface composition. The surface energy of the coatings estimated by the Van Oss approach was always lower than that estimated by the Kaelble approach. Colloidal interactions between pigment–pigment and/or pigment–binder were thought to play an essential role in determining the final coating surface energy and its components. Changes in the surface latex content and the surface energy due to the different pigment blends investigated were found to fit straight-line equations.     

Exploiting the synergy between coordination chemistry and molecular imprinting in the quest for new catalysts

The synthesis of transition metal active sites by the molecular imprinting of polymerizable metal complexes into highly cross-linked organic polymers is described. The emphasis of this Account is on the synergy between the long-term goals associated with new catalyst development and the more short-term goal of addressing fundamental questions in coordination chemistry, particularly emphasizing stereochemistry and structure. An argument is presented that the latter is necessary for ultimately achieving the more difficult but more important goal of designer catalysts that achieve reaction selectivities and reactivities not obtainable with traditional homo- or heterogeneous catalysts.     

Study of interfacial kinetics for liquid-liquid systems—II: Intrinsic kinetics of the copper chelation reaction with an oxime-based reagent

The interfacial chelation of copper from copper sulfate-sulfuric acid solutions by the commerical oxime extractant LIX65N in toluene is studied using the liquid jet recycle reactor. The intrinsic initial rate of copper chelation by LIX65N is found to be represented in mol. cm^?2-sec^?1 by the expression R = $\text{1.22 × 10}{}^{\mathrm{?8}}\text{{Cu}{}^{\mathrm{2+}}\text{}[LIX65N]}\text{{H}{}^{\mathrm{+}}\text{} + 0.0288[LIX65N]}$ where {Cu²⁺} and {H⁺} are the cupric and hydrogen activities. The interfacial rate expression above is determined as free from diffusional contributions by using a numerical solution to model mass transfer with interfacial reaction in the LJRR. The above expression is selected on statistical and physical grounds from a set of models systematically generated from the most probable reaction pathways. The liquid jet technique has been shown to be an effective and accurate (±6% experimental error) technique for the study of liquid-liquid interfacial reactions.     

闪锌矿的机械活化储能对其溶解反应动力学的影响

以过渡态理论为基础,从理论上初步探讨了机械活化储能对闪锌矿溶出反应动力学的影响,认为在化学反应控制的溶出反应过程中,机械活化闪锌矿的速率常数k2与未活化矿的速率常数k1之比满足k2/k1≈exp(E/RT).     

次磷酸钠制备及反应动力学研究

探讨了一步法生产次磷酸钠的方法，可间歇生产，也可连续生产，并将有毒的副产物PH3转变成目的产品次磷酸钠。最佳反应条件：反应温度70℃；黄磷，氢氧化钠和过氧化氢的摩尔比为2：2：1，反应时间为5h。此法可将产的收率从两步法的30％提高到71％以上。通过反应动力学研究可知，一步法生产次磷酸钠的总反应为一级反应，反应速率常数为k=111519exp(-40697.3/RT)。     

The role of the surface complex in the kinetics of the reaction of oxygen with carbon

Using thin films of pyrolytic carbon the kinetics of the reaction with oxygen were studied in a static system over the temperature range 748–1173 K at pressures in the neighborhood of l Torr (0.13 kPa). The formation of the stable surface complex, measured by pressure change and by temperature-programmed desorption, and products carbon monoxide and carbon dioxide were monitored as a function of reaction time during the complete course of the reaction. At lower temperatures an induction period was observed for formation of carbon monoxide and carbon dioxide but not for formation of the complex. The presence of the complex on the surface before the start of a reaction shortened the induction period and increased slightly the over-all rate. It was concluded that the surface complex is an intermediate in the production of carbon monoxide and carbon dioxide. A mechanism for the reaction is proposed which involves secondary reaction of oxygen with the complex and which accounts qualitatively for the kinetics of the reaction. It is suggested that a turn-over number may be estimated based on a number of active carbon atoms on the surface.     

Apparent kinetics of nonisothermal high temperature oxidative degradation of ethylene homopolymers: effects of residual catalyst surface chemistry and structure

The effects of two supported residual catalysts—one Ziegler-Natta and another metallocene—on the nonisothermal thermooxidative degradation of the resulting ethylene homopolymers were investigated using TGA experiments and kinetic modeling. The rigorous constitutive kinetic model (developed in this study), unlike the analytical Horowitz and Metzger model, fitted very well to the entire TGA curve, without distribution of activation energy E _a , for n (overall degradation order)?=?1 for both polymers. Neither n nor E _a varied as a function of fractional weight loss of the polymer. Hence, the proposed unified molecular level concept of surface chemistry and structure of the residual catalysts held all through the degradation process. The above feature of n and E _a also indicates the suitability of the model formulation and the effectiveness of the parameter-estimation algorithm. Random polymer chain scission, with the cleavage of the ?C?C? and the ?O?O? (hydroperoxide) bonds, prevailed. The types of residual catalyst surface chemistry and structure varied the bond cleavage process. The metallocene Zr residual catalyst caused more thermooxidative degradation in MetCat?HomoPE than what the Ti one did in Z-N?HomoPE. The rigorous constitutive model-predicted apparent kinetic energy E _a , and frequency factor Z also support this finding. The proposed degradation mechanism suggests that the Zr residual catalyst more (i) decreased the activation energy required to decompose the ?C?C? and the ?O?O? bonds, and (ii) eliminated β-hydrogen (by the carbonyl functionalities) from the polymer chains. These findings were attributed to the differences in surface chemistry and structure of the residual catalysts. Therefore, the current study presents a rigorous constitutive kinetic model that duly illustrates the influence of the characteristic surface chemistry and structure of the residual catalysts on the high temperature oxidative degradation of polyethylenes.     

Computational simulation of the dynamics of secondary organic aerosol formation in an environmental chamber

A key atmospheric process that is studied in laboratory chambers is the oxidation of volatile organic compounds to form low volatility products that condense on existing atmospheric particles (or nucleate) to form organic aerosol, so-called secondary organic aerosol. The laboratory chamber operates as a chemical reactor, in which a number of chemical and physical processes take place: gas-phase chemistry, transport of vapor oxidation products to suspended particles followed by uptake into the particles, deposition of vapors on the walls of the chamber, deposition of particles on the walls of the chamber, and coagulation of suspended particles. Understanding the complex interplay among these simultaneous physicochemical processes is necessary in order to interpret the results of chamber experiments. Here we develop and utilize a comprehensive computational model for dynamics of vapors and particles in a laboratory chamber and analyze chamber behavior over a range of physicochemical conditions.

Copyright © 2018 American Association for Aerosol Research     

Adiabatic correction for the esterification of acetic anhydride by methanol via accurate kinetics

In the field of adiabatic correction for complex reactions, a simple one-stage kinetic model was used to estimate the real reaction kinetics. However, this assumption simplified the real process, inevitably generated inaccurate or even unsafe results. Therefore, it was necessary to find a new correction method for complex reactions. In this work, esterification of acetic anhydride by methanol was chosen as an object reaction of study. The reaction was studied under different conditions by Reaction Calorimeter (RC1). Then, Thermal Safety Software (TSS) was used to establish the kinetic model and estimate the parameters, where, activation energies for three stages were 67.09, 81.02, 73.77 kJ·mol^-1 respectively, and corresponding frequency factors in logarithmic form were 16.05, 19.59, 15.72 s^-1. In addition, two adiabatic tests were performed by Vent Sizing Package2 (VSP2). For accurate correction of VSP2 tests, a new correction method based on Enhanced Fisher method was proposed. Combined with kinetics, adiabatic correction of esterification reaction was achieved. Through this research, accurate kinetic parameters for a three-step kinetic model of the esterification reaction were acquired. Furthermore, the correlation coefficients between simulated curves and corrected curves were 0.976 and 0.968, which proved the accuracy of proposed new adiabatic correction method. Based on this new method, conservative corrected results were able to be acquired and be applied in safety assessment.     

Dairy biofilm: an investigation of the impact on the surface chemistry of two materials: silicone and stainless steel

Biofilms are the most common mode of bacterial growth in nature and the formation will occur on organic or inorganic solid surfaces in contact with a liquid. The aims of this study were, by combining numeration and sessile drop technique, (i) to characterize the structural dynamics of dairy biofilm growth and the physico chemical properties on silicone and stainless steel and (ii) to evaluate the impact of bio-adhesion on chemistry of surfaces at different times of contact (2, 7, 9 and 24?h). Significantly, greater biofilm volumes were observed after 48?h on two materials. Gram-positive bacteria and fungal population exhibited a significantly higher biofilm organization than gram-negative (43–64%). Elsewhere, after 48?h, results showed a slight difference on gram-negative adhered cells on stainless steel than silicone (2.6?×?10⁷?cfu/cm² and 4.7?×?10⁵?cfu/cm², respectively). Moreover, the physico chemical properties of the surfaces showed that the silicone and stainless steel have a hydrophobic character (Giwi?=??68.28?mJ/m² and ?57.6?mJ/m², respectively). Also, both the surfaces present a weak electron donor character (γ ^??=?2.2?mJ/m² and 4.1?mJ/m², respectively). The real-time investigation of the impact of dairy biofilm on the physico chemical properties of the materials has shown a decrease of hydrophobicity degree of the silicone surface that becomes hydrophilic (ΔGiwi?=?11.47?mJ/m²) after 7?h and the increase of electron donor character (γ ^??=?75.8?mJ/m²). Elsewhere, bio-adhesion on stainless steel was accompanied with a decrease of hydrophobicity degree of the surface, which becomes hydrophilic after 7?h of contact (ΔGiwi?=?6.62?mJ/m²) and the increase of the electron donor character (γ ^??=?44.8?mJ/m²). While, after 24?h of contact, results showed a decrease of the hydrophilicity degree and surface energy components of silicone and stainless steel that become hydrophobic (ΔGiwi?=??21.2?mJ/m² and ΔGiwi?=??56.51?mJ/m², respectively) and weak electron donor (γ ^??=?14.0 and 2.3?mJ/m², respectively).     

Computational fluid dynamics simulations of heat transfer between the dense‐phase of a high‐temperature fluidized bed and an immersed surface

The transient process of heat transfer between a high‐temperature emulsion packet and the wall of an immersed surface is simulated using computational fluid dynamics (CFD). From these simulations, the total heat transfer coefficient and its radiant contribution due to the emulsion (dense) phase are evaluated. The results are compared with experimental data (Ozkaynak et al., “An experimental investigation of radiant heat transfer in high temperature fluidized beds,” in Fluidization IV, 1983:371–378) and with predicted values from the generalized heterogeneous model (GHM), (Mazza et al., “Evaluation of overall heat transfer rates between bubbling fluidized beds and immersed surfaces,” Chem Eng Commun., 1997;162:125–149). The CFD simulations are in good agreement with both, experimental data and theoretical GHM predictions and provide a reliable way to quantify the studied heat transfer process. Also, the GHM is validated as a practical tool to this end. © 2011 American Institute of Chemical Engineers AIChE J, 58: 412–426, 2012