Kinetics and Mechanism of the Reaction Between Zinc Oxide and Aluminum Oxide

Quantitative X-ray diffraction methods were used to define the kinetics of spinel formation. Diffusion controlled reaction rate constants were calculated on the basis of the reaction models of Jander, Dunwald-Wagner, Valensi, Zhuravlev et al. , Ginstling-Brounshte'n, and Kroger-Ziegler. The model proposed by Valensi is valid for describing solid-solid reaction rates in the later stages of the reaction. Inert markers indicated that diffusion of zinc ions through the spinel layer is the rate controlling mechanism. The activation energy for the process is 54,200 cal/mole. In the early stages of the reaction there is a second-order phase boundary kinetic process with an activation energy of 28,700 cal/ mole. The rate of chemical combination at the zinc-oxide-spinel phase boundary is believed to be rate controlling.     

碱金属碳酸盐对CaO高温固硫促进作用的研究

提高 ＣａＯ的固硫是对煤炭燃烧污染防治的研究热点．采用热天平测试研究在 ＣａＯ中添加不同碳酸盐的固硫反应的进程,并采用等效粒子模型处理实验数据,计算了表面化学反应控制阶段及产物层扩散控制阶段的动力学参数．实验及计算结果表明, ＣａＯ固硫反应初期为表面化学反应控制阶段,后期转为产物层扩散控制阶段．以碱金属碳酸盐为催化剂,能使固硫反应前期的化学反应控制阶段的反应活化能下降,并按 Ｌｉ, Ｎａ, Ｋ, Ｃｓ的顺序依次递减．将不同的碳酸盐作为固硫促进剂的 ＣａＯ加入型煤中,都得到了较高的固硫效率．     

Evaluation of the shrinking‐core model for examining the kinetics of film formation in a reactive latex blend

We prepared reactive latex blends from two copolymer latices comprised of n‐butyl methacrylate (n‐BMA) with acetoacetoxyethyl methacrylate and n‐BMA/dimethylaminoethyl methacrylate to study the kinetics of film formation. We generated thin films by blending equal weights of the two latices. The films were then cured at temperatures ranging from 50 to 90°C. The extent of the crosslinking reaction was calculated from the crosslink density, which was determined from swelling measurements of the films in toluene. The shrinking‐core model, a diffusion/reaction model, which was originally derived for combustion reactions of coal particles, was adopted to calculate the diffusion coefficient (D_e) and reaction rate constants from the extent of the reaction with time data. This model system exhibited a diffusion‐controlled regime above 70°C and a reaction‐controlled regime at temperatures below 70°C. In the reaction‐controlled regime, the shrinking‐core model predicted D_e for the system, which was in agreement with literature values for n‐BMA. In the diffusion‐controlled regime, the model predicted a lower apparent value for D_e but with an activation energy that was close to that obtained for n‐BMA. The model was also used to examine the kinetics of the crosslinking reaction. The kinetic rate constants for the crosslinking reaction were also determined. The activation energy for the crosslinking reaction was 18.8 kcal/mol, which compared reasonably with the activation energy of 22.8 kcal/mol determined for the reaction between the functional monomers as small molecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3659–3665, 2006     

Mathematical modeling of CO<Subscript>2</Subscript> removal using carbonation with CaO: The grain model

CaO carbonation with CO₂ is potentially a very important reaction for CO₂ removal from exhaust gas produced in power plants and other metallurgical plants and for hydrogen production by promoting water gas shift reaction in fossil fuel gasification. A mathematical model based on the grain model was applied for modeling of this reaction. Diffusion of gaseous phase through the product layer and structural change of the grains were considered in the model. The modeling results show that ignoring the reaction kinetics controlling regime in the early stage of the reaction and replacing it with a regime considering both the reaction kinetics and diffusion can generate good simulation results. The frequency factor of the reaction rate equation and the diffusivity of CO₂ through the CaCO₃ layer were justified to get the best fit at different temperature range from 400 to 750 °C with respect to experimental data in the literature. The mathematical model switches to a pure diffusion controlling regime at final stage of reaction.     

在Mo-Bi-Ce/SiO_2催化剂上丁烯-2氧化脱氢的内扩散影响

用玻璃流动外循环无梯度反应器研究了Mo—Bi—Ce/SiO_2催化剂上丁烯-2氧化脱氢的内扩散影响.确定了催化剂的有效因子,多孔催化剂的有效因子随反应温度的升高而减小.在内扩散区域的反应活化能为丁烯-2扩散活化能、动力学区域反应活化能的算术平均值.在内扩散区域的丁烯氧化脱氢生成丁二烯的选择性用经验式描述.     

THE KINETICS OF COBALT AND NICKEL EXTRACTION USING HEHEHP

The kinetics of the extraction of cobalt and nickel using purified mono 2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester (HEHEHP) were studied using the Rotating Diffusion Cell (RDC) apparatus. The extraction of cobalt was Investigated over a wide range of cobalt concentration, extractant concentration, pH and temperature conditions. Nickel extraction was examined over a wide range of nickel concentrations.

The kinetic data were treated according to both interfacial and mass transfer with chemical reaction (MTWCR) models. The MTWCR model adequately described the kinetic data for both the cobalt and nickel extraction experiments. No variation of an interfacial model was adequate to describe the data. In the MTWCR model, the extraction rate was shown to be controlled by a mechanism involving diffusion of the extractant into the aqueous phase boundary layer with subsequent reaction involving the addition of the first ligand to the cobalt or nickel ion. This extraction mechanism was substantiated by supplementary results including the activation energy determination which indicated mixed diffusion and chemical reaction control, the significant measured rate of partition of the extractant to the aqueous phase, and the values of the cobalt and nickel complex formation constants in the aqueous phase.     

5709萃取钴的宏观动力学研究

采用改进的恒界面池进行了异已基膦酸(1-甲基-庚基)酯(国内代号5709)-庚烷体系从硫酸介质中萃取钴(Ⅱ)的动力学研究.以组分活度代替浓度处理实验数据对有关参数进行了关联,并建立了相应的数学模型(?)=1.435×10~(-3)(a_c_o)-b[(a_(HA)_2)_b]~(1/2)·N~(1/2)/2.55×10~3(a_(H)_b·N~(1/2)+[(a_(HA)_2)_b]~(1/2)实验结果表明,5709萃取钴(Ⅱ)动力学的过程控制为混合控制机制,即为水相中钴离子的扩散和相界面钴的1—2络合物生成的化学反应为主要控制步骤.在水相pH值较高时,控制步骤以前者为主导;在水相pH值较低时,则以后者为主要控制步骤.     

Kinetic model of CaO/fly ash sorbent for flue gas desulphurization at moderate temperatures

Characteristics of the sulphation reaction between SO₂ and CaO/fly ash sorbent were analyzed based on TGA results to develop a kinetic model for a dry moderate temperature (400–800 °C) FGD process. It was found that SO₂ diffusion within sorbent particles involved three sub-processes: inter-particle diffusion, inter-grain diffusion and diffusion through product layers and the diffusion dominated the whole sulphation reaction process. The activation energy for product layer diffusion E_diff of 49.3 kJ mol⁻¹ being greater than the chemical reaction activation energy E_a of 13.9 kJ mol⁻¹ verified the importance of the diffusion. Predictions using the kinetic model in which k₀ varies with temperature agree well with the experimental data.     

A kinetic model of nano‐CaO reactions with CO2 in a sorption complex catalyst

This article describes the reactive kinetics of nano‐CaO with CO₂ in a sorption complex catalyst. Based on an observation of nano‐CaO reaction with CO₂ has a fast surface reaction regime and followed by a slow diffusion‐controlled regime, a criterion has been proposed to divide the fast surface reaction regime and the slow diffusion‐controlled reaction regime. The kinetics of the fast surface reaction was studied, and a new ion reaction mechanism was proposed. A surface reaction‐controlled kinetic model with a Boltzmann equation, X = X_u?X_u/[1+exp((t?t₀)k/X_u)], was developed. Experiments using nano‐CaO to react with CO₂ in a fast surface reaction regime within a sorption complex catalyst were performed using thermogravimetric analysis at 773–873 K under a N₂ atmosphere with 0.010–0.020 MPa CO₂. The activation energy of the kinetic model for carbonation is 30.2 kJ/mol, and the average relative deviation of the sorption ratio is less than 9.8%. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

强酸性离子交换树脂催化合成乙酸正丁酯动力学

为了获得D072型强酸性离子交换树脂催化剂合成乙酸正丁酯反应动力学方程,在间歇釜式反应器中,消除内外扩散后,测定不同反应条件下乙酸浓度随时间的变化,反应体系按拟均相处理,用初始速率法回归估算动力学模型参数。在催化剂平均粒度小于0.074 mm,搅拌速度大于150 r min 1时,可基本消除内外扩散的影响。在常压,催化剂用量为0.01665～0.08333 gcat gA 1,温度为326.2~358.2 K的条件范围,获得的动力学模型参数为:k0=8.86×104L mol 1 min 1 gcat 1,Ea=60728.86 J mol 1,平衡常数受温度的影响不大。在实验条件范围对获得的动力学方程进行了验证,最大相对偏差小于8.3%%,计算值与实验值符合较好。     

水蒸气对煅烧石灰石碳酸化反应影响的实验与模型分析

利用热重分析仪,对比了不同反应温度、不同水蒸气浓度对煅烧石灰石碳酸化反应的影响。碳酸化反应温度在500℃时,反应初期水蒸气对碳酸化反应的影响并不明显,反应10 min之后,在含有1.5%、10%和20%(体积分数)水蒸气条件下碳酸化转化率比无水蒸气条件下转化率分别提高了19.8%、27.2%和30.5%。水蒸气的存在有助于提高碳酸化反应转化率,但随着水蒸气浓度的增加转化率增加幅度减小。利用随机孔隙模型,对产物层扩散阶段扩散系数及反应活化能进行了计算。高温条件下,气氛中含有1.5%的水蒸气使反应活化能从237.7 kJ·mol^-1降低到179.9 kJ·mol^-1,提高水蒸气浓度到10%和20%后,反应活化能从156.6 kJ·mol^-1降低到148.6 kJ·mol^-1。不同水蒸气浓度条件下,碳酸化反应存在两个明显特征:一是大约在550℃处存在一个明显扩散系数的斜率变化,这一温度与气氛中是否存在水蒸气无关;另一特征是随着反应温度的提高,水蒸气的促进作用减弱。依据实验和模型计算结果,推测了当反应处于产物层扩散阶段时水蒸气对碳酸化反应影响的作用机理。     

The electrochemistry and kinetics of the silver-triiodide reaction

The oxidation reaction between silver and aqueous triiodide solutions was studied using both electrochemical and kinetic techniques. Electrochemical measurements of cathodic and anodic polarisation curves were undertaken, the results indicating that the reaction should be diffusion controlled. The kinetics were determined using the rotating disc method and the reaction rate was found to be first order in the triiodide concentration with rate constants approximately proportional to the square root of the rotation speed. This is also consistent with the reaction rate being controlled by the rate of diffusion of triiodide ions to the surface of the rotating silver disc. Temperature dependence studies supported this conclusion giving an activation energy of 16 ± 3 kJ mol_?1. Discrepancies between the kinetic rate constants and those calculated from the electrochemical measurements were attributed to roughness of the product layer.     

明胶层中的扩散和反应的动力学研究——(Ⅳ)扩散伴随油珠界面反应的动力学数值模型

设计了一个数值模型来模拟一个反应物在明胶层中边扩散边在油珠界面上与另一个反应物反应的动力学过程。提出了处理油珠界面反应的动力学方程,并应用在模型设计中。采用模型模拟与动力学实验测量相结合的方法不仅可以获得反应物在明胶层中的扩散系数和界面反应的比速率常数等重要动力学参数,而且可以提供反应物和生成物在明胶层中的时空分布,并预测不同条件下的动力学过程。对模型的适用性也作了详细的讨论。     

Kinetics and Mechanism of the Reaction Between Zinc Oxide and Barium Carbonate

The kinetics of reaction between BaCO₃ and ZnO were studied using thermogravimetric analysis to monitor the percent reaction versus time. Solid state reaction models based on ( a ) product growth controlled by diffusion through a continuous product layer, ( b ) product growth controlled by phase boundary reactions, and ( c ) the concept of an order of reaction, were invalid for the reaction studied. The kinetics of the reaction were described by the kt =–ln (1 – x )⅔ nuclei growth equation. The defect nature of the zinc oxide studied was altered by doping with Li2_O and Cr₂O₃. The activation energy for the reaction of BaCO₃ and pure ZnO was 54.6 kcal/mole. The changes in activation energy with the type and amount of ZnO doping cannot be accounted for by the quasi-chemical theory of solids.     

Direct Sulfation of Calcium Carbonate Using the Variable Diffusivity Approach

The direct sulfation of calcium carbonate was investigated in the temperature range of 600–900 °C under atmospheric pressure. Thermogravimetric analysis was employed to study the direct sulfation reaction. A gas mixture containing 3300 ppm sulfur dioxide in 5 vol.‐% oxygen and 95 vol.‐% carbon dioxide was passed through 3–5 mg of sorbent. The influence of particle size was studied using three different levels of particle average diameter. A variable diffusivity shrinking core model was applied to interpret the time‐conversion data. The conversion dependent effective diffusivity in the porous sulfated layer was estimated based on the two mechanisms in series, i.e., pore diffusion and solid product layer diffusion. By applying the activation energy data for chemical reaction, available in the literature, the reaction rate constant, and the solid product layer diffusivity with Arrhenius type temperature dependency were estimated as adjustable parameters. The variation of fractional conversion with time can be reasonably predicted by using the developed model and the estimated parameters.     

Investigations on the kinetics and mechanisms of sorptive removal of fluoride from water using alumina cement granules

This paper examines the kinetics of fluoride removal from water by the adsorbent alumina cement granules (ALC), exploring the mechanisms involved. ALC exhibited a biphasic kinetic profile of sorption with an initial rapid uptake phase followed by a slow and gradual phase. The kinetic profile has been modeled using pseudo-first-order model, pseudo-second-order model, intraparticle diffusion model and Elovich model. The kinetic sorption profiles offered excellent fit with pseudo-second-order model with a high R² value of 0.9987. The value of activation energy of the system (17.67 kJ mol⁻¹) indicates the significance of diffusion in the sorption process. The rate-limiting step of sorption was evaluated by analyzing the response of the system to pH, inert electrolyte concentration, and desorption pattern of the adsorbent, instead of assigning it to a single kinetic model. Accordingly, the surface reactions involving the heterogeneity of the surface site bonding energy or other reactions occurring on the surface of ALC were found predominant in defining the rate-limiting step. The dominant mechanism of fluoride removal appeared to be a chemisorptive ligand exchange reaction involving the formation of inner-sphere complexation of fluoride with ALC.     

两种煤焦油沥青恒温热转化过程研究

通过对两种煤焦油沥青恒温热转化过程的研究,得出了中间相转化的特征时间和动力学参数,试验表明,在中间相产率约１５％之前,主要产生中间相小球体的生成反应,活化能较高,而后期反应活化能较低。     

Formation of calcium plumbate: Kinetics and mechanism of reaction

In the presence of excess air the kinetics of reaction between CaO and PbO to form calcium plumbate are governed by the diffusion process described by Jander's kinetic model. The energy of activation of the process, as calculated from the Arrhenius equation, is 50 kcal/mol. In an air and nitrogen atmosphere (ratio 1:16) the reaction rate is 4–5 times slower. It has been shown that formation of calcium plumbate from pure CaO and PbO takes place between 600–800° without formation of intermediate compounds. From the results obtained it is deduced that the mechanism of formation consists of two main stages–diffusion between the CaO and PbO, substantially due to the more diffusible PbO, and chemical reaction in the presence of O₂.     

Reactions of solid particles with nonuinform distribution of solid reactant: The volume reaction model

The effect of non-uniform solid reactant distribution on conversion of solid particles in gas-solid reactions is analyzed based on the volume reaction model. Certain special features of such systems are pointed out. The possibility of ash layer formation in the kinetically controlled regime is discussed. Conditions leading to single or double ash layer formation, both at the center and surface of the particle, in the intermediate regime of diffusion with simultaneous reaction are described. Detailed mathematical equations which are useful for calculation of the conversion-time relationship for particles with non-uniform solid reactant distribution are presented. Comparison is made to reaction of uniform particles and differences in required reaction time for desired conversion are outlined.     

Kinetic analysis of spinel formation from powder compaction of magnesia and alumina

A kinetic investigation into the formation of spinel from alumina (Al₂O₃) and magnesia (MgO) powder compaction with a stoichiometric mixing molar ratio of 1:1 was conducted in the temperature range of 1573 K to 1773 K over a certain time interval up to 25 h. The samples were pressed at pressures of 125, 375 and 750 MPa. The progress of the reaction was evaluated by monitoring the expansion ratio instead of the thickness of the spinel layer that was generated. The expansion ratio increases with increasing pressing pressure and holding time, and high temperature favored spinel formation. However, densification was observed at temperatures above 1673 K due to the occurrence of sintering between the powders. A kinetic model taking electrochemical potential as the driving force of the reaction was established, and the apparent activation energy was calculated to be 310.6 kJ/mol in the temperature range between 1573 K and 1673 K. The reaction was controlled by the inter-diffusion of Al³⁺ and Mg²⁺ ions in the spinel layer that was formed.