This paper represents an attempt to extend the mechanisms of reactions and kinetics of a methane combustion reaction.Three saddle points(SPs) are identified in the reaction CH_4+ O(~3P) → OH + CH_3 using the co...This paper represents an attempt to extend the mechanisms of reactions and kinetics of a methane combustion reaction.Three saddle points(SPs) are identified in the reaction CH_4+ O(~3P) → OH + CH_3 using the complete active space selfconsistent field and the multireference configuration interaction methods with a proper active space. Our calculations give a fairly accurate description of the regions around the twin first-order SPs(~3A' and ~3A〞) along the direction of O(~3P) attacking a near-collinear H–CH_3. One second-order SP^(2nd)(~3E) between the above twin SPs is the result of the C_(3v) symmetry Jahn–Teller coupling within the branching space. Further kinetic calculations are performed with the canonical unified statistical theory method with the temperature ranging from 298 K to 1000 K. The rate constants are also reported. The present work reveals the reaction mechanism of hydrogen-abstraction by the O(~3P) from methane, and develops a better understanding for the role of SPs. In addition, a comparison of the reactions of O(~3P) with methane through different channels allows a molecule-level discussion of the reactivity and mechanism of the title reaction.展开更多
The oxide-zeolite process provides a promising way for one-step production of aromatics from syngas,whereas the reasons for the dramatic effect of intimacy between oxide and zeolite in the composite catalyst on the pr...The oxide-zeolite process provides a promising way for one-step production of aromatics from syngas,whereas the reasons for the dramatic effect of intimacy between oxide and zeolite in the composite catalyst on the product selectivity are still unclear. In order to explore the optimal intimacy and the essential influence factors, ZnCrOxcombined with ZSM-5 are employed to prepare the composite catalysts with different distances between the two components by changing the mixing methods. An aromatic selectivity of 74%(with CO conversion to be 16%) is achieved by the composite catalyst when the intimacy is in the range of nanometer. A so-called ‘iterative reactions’ mechanism of intermediates over oxides is then proposed and studied: the intermediate chemical can undergo a hydrogenation reaction on oxide.So the shorter the intermediates stay on oxide, the more of chance for C-C coupling takes place on zeolite to form aromatics. Moreover, the aero-environments of reaction is found to impact on the extent of iterative reaction as well. Therefore, when the intimacy between the two components changes, the extent of iterative reactions vary, resulting in alteration of product distribution. This work provides new insight in understanding the mechanisms during the complex process of OX-ZEO composite catalysis and sheds light to the design of a high-yield catalyst for synthetization of aromatics from syngas.展开更多
To more comprehensively analyze the effect of CO_2 and H_2O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO_2 and H_2O using high temperature gas–solid reaction appar...To more comprehensively analyze the effect of CO_2 and H_2O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO_2 and H_2O using high temperature gas–solid reaction apparatus over the range of 950–1250°C were studied, and the thermodynamic and kinetic analyses were also performed. The results show that the average reaction rate of coke with H_2O is about 1.3–6.5 times that with CO_2 in the experimental temperature range. At the same temperature, the endothermic effect of coke with H_2O is less than that with CO_2. As the pressure increases, the gasification dissolution reaction of coke shifts to the high-temperature zone. The use of hydrogen-rich fuels is conducive to decreasing the energy consumed inside the blast furnace, and a corresponding high-pressure operation will help to suppress the gasification dissolution reaction of coke and reduce its deterioration. The interfacial chemical reaction is the main rate-limiting step over the experimental temperature range. The activation energies of the reaction of coke with CO_2 and H_2O are 169.23 kJ ·mol-1 and 87.13 kJ·mol^(-1), respectively. Additionally, water vapor is more likely to diffuse into the coke interior at a lower temperature and thus aggravates the deterioration of coke in the middle upper part of blast furnace.展开更多
The mechanism, catalytic effect and substituent effect of the hetero-Diels-Alder reactions between phosphonodithioformate and butadienes have been investigated theoretically using density functional theory at the B3LY...The mechanism, catalytic effect and substituent effect of the hetero-Diels-Alder reactions between phosphonodithioformate and butadienes have been investigated theoretically using density functional theory at the B3LYP/6-31G(d) level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C and opposite result is found in other reactions. The BF3 catalyst and trimethylsilyloxy group may lower the activation barriers by changing the energies of FMOs for reactant molecules. With the BF3-catalyzed reactions, the complete regioselectivity observed experimentally has well been reproduced by theoretical calculation and these results originate probably from blue-shifting C-H...F hydrogen bond interaction in some transition states.展开更多
The orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore with NaOH aiming to comprehensively utilize zinc oxide ore.The optimized reaction conditions were molar ratio of NaOH to zinc...The orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore with NaOH aiming to comprehensively utilize zinc oxide ore.The optimized reaction conditions were molar ratio of NaOH to zinc oxide ore 6:1,roasting temperature 450°C,holding time 150 min.The molar ratio of NaOH to zinc oxide ore was the most predominant factor affecting the extraction ratios of zinc oxide and silica.The mineral phase transformations were investigated by testing the phases of specimens obtained at different temperatures.The process was that silica reacted with molten NaOH to form Na_2SiO_3 at first,then transformed into Na_4SiO_4 with temperature rising.ZnCO_3 and its decomposing product ZnO reacted with NaOH to form Na_2ZnO_2.Na_2ZnSiO_4was also obtained.The reaction rate was investigated using unreacted shrinking core model.Two models used were chemical reaction at the particle surface and diffusion through the product layer.The results indicated that the reaction rate was combine-controlled by two models.The activation energy and frequency factor were obtained as 24.12 k J/mol and 0.0682,respectively.展开更多
An orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore using(NH_4)_2SO_4. The optimized reaction conditions are defined as an(NH_4)_2SO_4/zinc molar ratio of 1.4:1, a roasting ...An orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore using(NH_4)_2SO_4. The optimized reaction conditions are defined as an(NH_4)_2SO_4/zinc molar ratio of 1.4:1, a roasting temperature of 440°C, and a thermostatic time of 60 min. The molar ratio of(NH_4)_2SO_4/zinc is the most predominant factor and the roasting temperature is the second significant factor that governs the zinc extraction. Thermogravimetric-differential thermal analysis was used for(NH_4)_2SO_4 and zinc mixed in a molar ratio of 1.4:1 at the heating rates of 5, 10, 15, and 20 K·min-1. Two strong endothermic peaks indicate that the complex chemical reactions occur at approximately 290°C and 400°C. XRD analysis was employed to examine the transformations of mineral phases during roasting process. Kinetic parameters, including reaction apparent activation energy, reaction order, and frequency factor, were calculated by the Doyle-Ozawa and Kissinger methods. Corresponding to the two endothermic peaks, the kinetic equations were obtained.展开更多
The prepolymerization and curing reaction kinetics of polyurethane/montmorillonite have been studied with end group analysis and FTIR respectively. It was found that the prepolymerization and curing reaction followed ...The prepolymerization and curing reaction kinetics of polyurethane/montmorillonite have been studied with end group analysis and FTIR respectively. It was found that the prepolymerization and curing reaction followed the 2nd-order kinetics. But the activation energy of prepolymerization increased from 42.7 kJ/mol to 56.5 kJ/rnol after the montmorillonite was added in the reaction system, and activation energy of curing reaction decreased from 64.4 kJ/mol to 17.5 kJ/mol. 2007 Bing Liao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
Based on the measurement of the released hydrogen gas pressure (PH2), the reaction kinetics between TiH2 powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of...Based on the measurement of the released hydrogen gas pressure (PH2), the reaction kinetics between TiH2 powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of TiH2 powder and aluminum melt was studied. The results show that the-time curves have three regions; in the first and second regions, the rate of reaction conforms zero and one order, respectively; in the third region, the hydrogen gas pressure remains constant and the rate of reaction reaches zero. The main factors that control the rate of reaction in the first and second regions are the penetration of hydrogen atoms in the titanium lattice and the chemical reaction between molten aluminum and titanium, respectively. According to the main factors that control the rate of reaction, three temperature ranges are considered for the reaction mechanism: (a) 700-750°C, (b) 750-800°C, and (c) 800-1000°C. In the first temperature range, the reaction is mostly under the control of chemical reaction; at the temperature range of 750 to 800°C, the reaction is controlled by the diffusion and chemical reaction; at the third temperature range (800-1000°C), the dominant controlling mechanism is diffusion.展开更多
Time-dependent quantum wave packet calculations were carried out for the F + HBr reaction on the latest London-Erying-Polanyi-Sato potential energy surface constructed by Persky et al. The calculated reaction probabi...Time-dependent quantum wave packet calculations were carried out for the F + HBr reaction on the latest London-Erying-Polanyi-Sato potential energy surface constructed by Persky et al. The calculated reaction probabilities dramatically increase near the zero collision energy and then slightly decrease with increasing collision energy, which corresponds well to the behavior of a barrierless reaction. The effects of reagent HBr excitation were examined, it is shown that both the vibrational and the rotational excitations of reagent HBr have a negative effect on the reactivity of F + HBr. The integral cross-section for the ground state of the reagent HBr decreases at a low collision energy and then becomes plat with increasing collision energy, which is reasonable for the feasibility of such an exothermal reaction. The rate constant that was obtained is slightly higher than that obtained in the quasi-classical trajectory calculation.展开更多
M, a particular industrial waste, was selected to detoxify chromium slag at a high temperature. The carbon remaining in M reduced Cr ( Ⅳ ) of Na2 CrO4 borne in the chromium slag to Cr ( Ⅲ ) in the solid phase re...M, a particular industrial waste, was selected to detoxify chromium slag at a high temperature. The carbon remaining in M reduced Cr ( Ⅳ ) of Na2 CrO4 borne in the chromium slag to Cr ( Ⅲ ) in the solid phase reaction, and its thermodynamics and kinetics were studied. The reduction process of Na2CrO4 by carbon produced CO, whiCh'was endothermic. Under the experimental condition, the apparent activation energy was 4. 41 kJ·mol^-1 , the'apparent order of reaction for Na2 CrO4 was equal to one, and the partial pressure of CO was only 0.22 Pa at 1 330℃.展开更多
The in situ synthesis method for titanium matrix composites (TMCs) has obvious technical and economical advantages over other traditional methods. Ultrafine reinforcement particles were formed in situ by chemical re...The in situ synthesis method for titanium matrix composites (TMCs) has obvious technical and economical advantages over other traditional methods. Ultrafine reinforcement particles were formed in situ by chemical reaction between elements or between elements and compounds. Using the approach, contamination at the composite matrix/reinforcement particle interface did not occur, interface bonding was good, and the reinforcement particle was thermodynamically stable. The stage of development of the preparation process for in situ TMCs as well as the thermodynamic analysis of the possible in situ reaction systems was described.展开更多
The effect of F,K,and Na on the solid phase reaction of the Baiyunebo iron ore was investigated by differential thermal analysis (DTA) and X-ray diffraction(XRD).It has been identified that alkaline elements K and...The effect of F,K,and Na on the solid phase reaction of the Baiyunebo iron ore was investigated by differential thermal analysis (DTA) and X-ray diffraction(XRD).It has been identified that alkaline elements K and Na in the Baiyunebo ore instigate the formation of low melting point compounds Na2SiO3 and Na2O·Fe2O3 and the generation of molten state in the solid phase sintering.Element F in the Baiyunebo ore facilitates the formation of cuspidine compound 3CaO·2SiO2·CaF2 in the solid phase reaction.The cuspidine compound is kept in solid as one of the final products through the entire sintering process due to its high melting point.In the sintering process,CaF2and SiO2 react with CaO first and form 3CaO·2SiO2·CaF2 and 3CaO·2SiO2,so the formation of ferrites,Na2O·Fe2O3,and 2CaO·Fe2O3 is inhibited.展开更多
The dehydrogenation reaction of H2S by the ^3Σ^- ground state of VS^+: VS^+ + H2S → VS2^+ + H2 has been studied by using Density Functional Theory (DPT) at the B3LYP/DZVP level. It is found that the reaction...The dehydrogenation reaction of H2S by the ^3Σ^- ground state of VS^+: VS^+ + H2S → VS2^+ + H2 has been studied by using Density Functional Theory (DPT) at the B3LYP/DZVP level. It is found that the reaction proceeds along two possible pathways (A and B) yielding two isomer dehydrogenation products VS2^+-1 (^3B2) and VS2^+-2 (^3A1), respectively. For both pathways, the reaction has a two-step-reaction mechanism that involves the migration of two hydrogen atoms from S2 to V^+, respectively. The migration of the second hydrogen via TS3 and that of the first via TS4 are the rate-determining steps for pathways A and B, respectively. The activation energy is 17.4 kcal/mol for pathway A and 22.8 kcal/mol for pathway B relative to the reactants. The calculated reaction heat of 9.9 kcal/mol indicates the endothermicity of pathway A and that of -11.9 kcal/mol suggests the exothermicity of pathway B.展开更多
Hydrogenation of carbazole and N-ethylcarbazole over Raney-Ni catalyst were realized in the temperature range of 393-503 K. 4[H] adduct dominated the hydrogenation products and the formation of 2[H] adduct was the rat...Hydrogenation of carbazole and N-ethylcarbazole over Raney-Ni catalyst were realized in the temperature range of 393-503 K. 4[H] adduct dominated the hydrogenation products and the formation of 2[H] adduct was the rate-limiting step during the period, in which the conversion of carbazole was less than 40%. The hydrogenation process followed pseudo-first-order kinetics and the hydrogenation activation energies of carbazole and N-ethylcarbazole were 90 kJ/mol and 115 kJ/mol, respectively. The reaction starting position as well as the pathway of the hydrogenation of (N-ethyl)carbazole were investigated by comparing the kinetic characteristics of hydrogen uptake of carbazole and N- ethylcarbazole. The results showed that the reaction was a stepwise hydrogenation process and the first H_2 was added to the C1 = C10 double bond in the hydrogenation.展开更多
Carbon supported gold-iridium composite(Au Ir/C) was synthesized by a facile one-step process and was investigated as the bifunctional catalyst for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). Th...Carbon supported gold-iridium composite(Au Ir/C) was synthesized by a facile one-step process and was investigated as the bifunctional catalyst for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The physical properties of the Au Ir/C composite were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). Although the Au and Ir in the Au Ir/C did not form alloy, it is clear that the introduction of Ir decreases the average Au particle size to 4.2 nm compared to that in the Au/C(10.1 nm). By systematical analysis on chemical state of metal surface via XPS and the electrochemical results, it was found that the Au surface for the Au/C can be activated by potential cycling from 0.12 V to 1.72 V, resulting in the increased surface roughness of Au,thus improving the ORR activity. By the same potential cycling, the Ir surface of the Ir/C was irreversibly oxidized, leading to degraded ORR activity but uninfluenced OER activity. For the Au Ir/C, Ir protects Au against being oxidized due to the lower electronegativity of Ir. Combining the advantages of Au and Ir in catalyzing ORR and OER, the Au Ir/C catalyst displays an enhanced catalytic activity to the ORR and a comparable OER activity. In the 50-cycle accelerated aging test for the ORR and OER, the Au Ir/C displayed a satisfied stability, suggesting that the Au Ir/C catalyst is a potential bifunctional catalyst for the oxygen electrode.展开更多
Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising...Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising catalysts for electrocatalytic reactions due to the earth-abundance and Pt-resembled electrical properties. In this work, taking the advantage of the interaction between the basic groups of the Mo(VI)-melamine polymer and the acidic groups on the surface of the oxidized carbon nanotubes(CNTs), N-doped CNTs supported Mo2C nanoparticles(Mo2C/NCNT) are prepared, which exhibit outstanding electrocatalytic activity and durability for both the hydrogen evolution and oxygen reduction reactions. The impressive performance of Mo2C/NCNT can be attributed to the small size of Mo2C particles, the large exposure ratio of surface sites and the presence of N-doped CNTs. This work enlarges the multi-field applications of molybdenum carbide-base materials as promising non-precious metal electrocatalysts, which is of great significance for sustainable energy-related technologies.展开更多
Wittig reactions of benzaldehydes, alkanals, and cycloalkanals as well as of acetophenones are carried out with alkoxycarbonyl methylidenetriphenylphosphoranes in 10 w% aqueous NaOH, where the cinnamates and alkenoate...Wittig reactions of benzaldehydes, alkanals, and cycloalkanals as well as of acetophenones are carried out with alkoxycarbonyl methylidenetriphenylphosphoranes in 10 w% aqueous NaOH, where the cinnamates and alkenoates produced are hydrolysed in situ and the corresponding acids are obtained after mostly simple extractive work-up, often without employing organic solvents. Under the same conditions, benzaldehydes are reacted with alkoxycarbonyl bromomethy-lidenephosphorane to produce 3-arylprop-2-ynoic acids (arylpropiolic acids).展开更多
Polymer electrolyte membrane fuel cells(PEMFCs), as an energy conversion technology, have attracted extensive attention due to their high conversion efficiency, low emission, high energy density,and fast fuel charging...Polymer electrolyte membrane fuel cells(PEMFCs), as an energy conversion technology, have attracted extensive attention due to their high conversion efficiency, low emission, high energy density,and fast fuel charging [1,2]. Pt-based catalysts have been acknowledged to be the most effective catalyst for the oxygen reduction reaction(ORR) [3–5]. However, both the source scarcity and high cost of Pt severely hinder the commercial application of the PEMFCs [1,6,7].展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51574016 and 51604018)
文摘This paper represents an attempt to extend the mechanisms of reactions and kinetics of a methane combustion reaction.Three saddle points(SPs) are identified in the reaction CH_4+ O(~3P) → OH + CH_3 using the complete active space selfconsistent field and the multireference configuration interaction methods with a proper active space. Our calculations give a fairly accurate description of the regions around the twin first-order SPs(~3A' and ~3A〞) along the direction of O(~3P) attacking a near-collinear H–CH_3. One second-order SP^(2nd)(~3E) between the above twin SPs is the result of the C_(3v) symmetry Jahn–Teller coupling within the branching space. Further kinetic calculations are performed with the canonical unified statistical theory method with the temperature ranging from 298 K to 1000 K. The rate constants are also reported. The present work reveals the reaction mechanism of hydrogen-abstraction by the O(~3P) from methane, and develops a better understanding for the role of SPs. In addition, a comparison of the reactions of O(~3P) with methane through different channels allows a molecule-level discussion of the reactivity and mechanism of the title reaction.
基金the National Key R&D Program of China(2016YFA0202804)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020400)+2 种基金the National Natural Science Foundation of China(Nos.21506204,21476226)Dalian Science Foundation for Distinguished Young Scholars(2016RJ04)the Youth Innovation Promotion Association CAS for financial support
文摘The oxide-zeolite process provides a promising way for one-step production of aromatics from syngas,whereas the reasons for the dramatic effect of intimacy between oxide and zeolite in the composite catalyst on the product selectivity are still unclear. In order to explore the optimal intimacy and the essential influence factors, ZnCrOxcombined with ZSM-5 are employed to prepare the composite catalysts with different distances between the two components by changing the mixing methods. An aromatic selectivity of 74%(with CO conversion to be 16%) is achieved by the composite catalyst when the intimacy is in the range of nanometer. A so-called ‘iterative reactions’ mechanism of intermediates over oxides is then proposed and studied: the intermediate chemical can undergo a hydrogenation reaction on oxide.So the shorter the intermediates stay on oxide, the more of chance for C-C coupling takes place on zeolite to form aromatics. Moreover, the aero-environments of reaction is found to impact on the extent of iterative reaction as well. Therefore, when the intimacy between the two components changes, the extent of iterative reactions vary, resulting in alteration of product distribution. This work provides new insight in understanding the mechanisms during the complex process of OX-ZEO composite catalysis and sheds light to the design of a high-yield catalyst for synthetization of aromatics from syngas.
基金financially supported by the National Natural Science Foundation of China (No. 51474002)the National Science Foundation for Young Scientists of China (No. 51304014)the Yong Elite Scientists Sponsorship Program by CAST (No. 2017QNRC001)
文摘To more comprehensively analyze the effect of CO_2 and H_2O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO_2 and H_2O using high temperature gas–solid reaction apparatus over the range of 950–1250°C were studied, and the thermodynamic and kinetic analyses were also performed. The results show that the average reaction rate of coke with H_2O is about 1.3–6.5 times that with CO_2 in the experimental temperature range. At the same temperature, the endothermic effect of coke with H_2O is less than that with CO_2. As the pressure increases, the gasification dissolution reaction of coke shifts to the high-temperature zone. The use of hydrogen-rich fuels is conducive to decreasing the energy consumed inside the blast furnace, and a corresponding high-pressure operation will help to suppress the gasification dissolution reaction of coke and reduce its deterioration. The interfacial chemical reaction is the main rate-limiting step over the experimental temperature range. The activation energies of the reaction of coke with CO_2 and H_2O are 169.23 kJ ·mol-1 and 87.13 kJ·mol^(-1), respectively. Additionally, water vapor is more likely to diffuse into the coke interior at a lower temperature and thus aggravates the deterioration of coke in the middle upper part of blast furnace.
文摘The mechanism, catalytic effect and substituent effect of the hetero-Diels-Alder reactions between phosphonodithioformate and butadienes have been investigated theoretically using density functional theory at the B3LYP/6-31G(d) level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C and opposite result is found in other reactions. The BF3 catalyst and trimethylsilyloxy group may lower the activation barriers by changing the energies of FMOs for reactant molecules. With the BF3-catalyzed reactions, the complete regioselectivity observed experimentally has well been reproduced by theoretical calculation and these results originate probably from blue-shifting C-H...F hydrogen bond interaction in some transition states.
基金Projects(51774070,51204054)supported by the National Natural Science Foundation of ChinaProject(N150204009)supported by the Ministry of Education Basic Scientific Research Business Expenses,ChinaProject(2007CB613603)supported by the National Basic Research Program of China
文摘The orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore with NaOH aiming to comprehensively utilize zinc oxide ore.The optimized reaction conditions were molar ratio of NaOH to zinc oxide ore 6:1,roasting temperature 450°C,holding time 150 min.The molar ratio of NaOH to zinc oxide ore was the most predominant factor affecting the extraction ratios of zinc oxide and silica.The mineral phase transformations were investigated by testing the phases of specimens obtained at different temperatures.The process was that silica reacted with molten NaOH to form Na_2SiO_3 at first,then transformed into Na_4SiO_4 with temperature rising.ZnCO_3 and its decomposing product ZnO reacted with NaOH to form Na_2ZnO_2.Na_2ZnSiO_4was also obtained.The reaction rate was investigated using unreacted shrinking core model.Two models used were chemical reaction at the particle surface and diffusion through the product layer.The results indicated that the reaction rate was combine-controlled by two models.The activation energy and frequency factor were obtained as 24.12 k J/mol and 0.0682,respectively.
基金financially supported by the National Natural Science Foundation of China(Nos.51204054 and 51574084)the Fundamental Research Funds for the Central Universities of China(No.N150204009)the National Basic Research Priorities Program of China(No.2014CB643405)
文摘An orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore using(NH_4)_2SO_4. The optimized reaction conditions are defined as an(NH_4)_2SO_4/zinc molar ratio of 1.4:1, a roasting temperature of 440°C, and a thermostatic time of 60 min. The molar ratio of(NH_4)_2SO_4/zinc is the most predominant factor and the roasting temperature is the second significant factor that governs the zinc extraction. Thermogravimetric-differential thermal analysis was used for(NH_4)_2SO_4 and zinc mixed in a molar ratio of 1.4:1 at the heating rates of 5, 10, 15, and 20 K·min-1. Two strong endothermic peaks indicate that the complex chemical reactions occur at approximately 290°C and 400°C. XRD analysis was employed to examine the transformations of mineral phases during roasting process. Kinetic parameters, including reaction apparent activation energy, reaction order, and frequency factor, were calculated by the Doyle-Ozawa and Kissinger methods. Corresponding to the two endothermic peaks, the kinetic equations were obtained.
文摘The prepolymerization and curing reaction kinetics of polyurethane/montmorillonite have been studied with end group analysis and FTIR respectively. It was found that the prepolymerization and curing reaction followed the 2nd-order kinetics. But the activation energy of prepolymerization increased from 42.7 kJ/mol to 56.5 kJ/rnol after the montmorillonite was added in the reaction system, and activation energy of curing reaction decreased from 64.4 kJ/mol to 17.5 kJ/mol. 2007 Bing Liao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
文摘Based on the measurement of the released hydrogen gas pressure (PH2), the reaction kinetics between TiH2 powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of TiH2 powder and aluminum melt was studied. The results show that the-time curves have three regions; in the first and second regions, the rate of reaction conforms zero and one order, respectively; in the third region, the hydrogen gas pressure remains constant and the rate of reaction reaches zero. The main factors that control the rate of reaction in the first and second regions are the penetration of hydrogen atoms in the titanium lattice and the chemical reaction between molten aluminum and titanium, respectively. According to the main factors that control the rate of reaction, three temperature ranges are considered for the reaction mechanism: (a) 700-750°C, (b) 750-800°C, and (c) 800-1000°C. In the first temperature range, the reaction is mostly under the control of chemical reaction; at the temperature range of 750 to 800°C, the reaction is controlled by the diffusion and chemical reaction; at the third temperature range (800-1000°C), the dominant controlling mechanism is diffusion.
基金Supported by the Open Project Program of Key Laboratory of Advanced Materials &Rheological Properties, Ministry of Educa-tion, China(No KF0504)
文摘Time-dependent quantum wave packet calculations were carried out for the F + HBr reaction on the latest London-Erying-Polanyi-Sato potential energy surface constructed by Persky et al. The calculated reaction probabilities dramatically increase near the zero collision energy and then slightly decrease with increasing collision energy, which corresponds well to the behavior of a barrierless reaction. The effects of reagent HBr excitation were examined, it is shown that both the vibrational and the rotational excitations of reagent HBr have a negative effect on the reactivity of F + HBr. The integral cross-section for the ground state of the reagent HBr decreases at a low collision energy and then becomes plat with increasing collision energy, which is reasonable for the feasibility of such an exothermal reaction. The rate constant that was obtained is slightly higher than that obtained in the quasi-classical trajectory calculation.
基金Item Sponsored by National Natural Science Foundation of China (50234040)
文摘M, a particular industrial waste, was selected to detoxify chromium slag at a high temperature. The carbon remaining in M reduced Cr ( Ⅳ ) of Na2 CrO4 borne in the chromium slag to Cr ( Ⅲ ) in the solid phase reaction, and its thermodynamics and kinetics were studied. The reduction process of Na2CrO4 by carbon produced CO, whiCh'was endothermic. Under the experimental condition, the apparent activation energy was 4. 41 kJ·mol^-1 , the'apparent order of reaction for Na2 CrO4 was equal to one, and the partial pressure of CO was only 0.22 Pa at 1 330℃.
基金This work was financially supported by the National Natural Science Foundation of China (No. 50205005)
文摘The in situ synthesis method for titanium matrix composites (TMCs) has obvious technical and economical advantages over other traditional methods. Ultrafine reinforcement particles were formed in situ by chemical reaction between elements or between elements and compounds. Using the approach, contamination at the composite matrix/reinforcement particle interface did not occur, interface bonding was good, and the reinforcement particle was thermodynamically stable. The stage of development of the preparation process for in situ TMCs as well as the thermodynamic analysis of the possible in situ reaction systems was described.
基金supported by the National Natural Science Foundation of China(No.50664006)
文摘The effect of F,K,and Na on the solid phase reaction of the Baiyunebo iron ore was investigated by differential thermal analysis (DTA) and X-ray diffraction(XRD).It has been identified that alkaline elements K and Na in the Baiyunebo ore instigate the formation of low melting point compounds Na2SiO3 and Na2O·Fe2O3 and the generation of molten state in the solid phase sintering.Element F in the Baiyunebo ore facilitates the formation of cuspidine compound 3CaO·2SiO2·CaF2 in the solid phase reaction.The cuspidine compound is kept in solid as one of the final products through the entire sintering process due to its high melting point.In the sintering process,CaF2and SiO2 react with CaO first and form 3CaO·2SiO2·CaF2 and 3CaO·2SiO2,so the formation of ferrites,Na2O·Fe2O3,and 2CaO·Fe2O3 is inhibited.
文摘The dehydrogenation reaction of H2S by the ^3Σ^- ground state of VS^+: VS^+ + H2S → VS2^+ + H2 has been studied by using Density Functional Theory (DPT) at the B3LYP/DZVP level. It is found that the reaction proceeds along two possible pathways (A and B) yielding two isomer dehydrogenation products VS2^+-1 (^3B2) and VS2^+-2 (^3A1), respectively. For both pathways, the reaction has a two-step-reaction mechanism that involves the migration of two hydrogen atoms from S2 to V^+, respectively. The migration of the second hydrogen via TS3 and that of the first via TS4 are the rate-determining steps for pathways A and B, respectively. The activation energy is 17.4 kcal/mol for pathway A and 22.8 kcal/mol for pathway B relative to the reactants. The calculated reaction heat of 9.9 kcal/mol indicates the endothermicity of pathway A and that of -11.9 kcal/mol suggests the exothermicity of pathway B.
基金supported by the National Natural Science Foundation of China(U1162127,U1462201,21076189,21476202 and 21276231)
文摘Hydrogenation of carbazole and N-ethylcarbazole over Raney-Ni catalyst were realized in the temperature range of 393-503 K. 4[H] adduct dominated the hydrogenation products and the formation of 2[H] adduct was the rate-limiting step during the period, in which the conversion of carbazole was less than 40%. The hydrogenation process followed pseudo-first-order kinetics and the hydrogenation activation energies of carbazole and N-ethylcarbazole were 90 kJ/mol and 115 kJ/mol, respectively. The reaction starting position as well as the pathway of the hydrogenation of (N-ethyl)carbazole were investigated by comparing the kinetic characteristics of hydrogen uptake of carbazole and N- ethylcarbazole. The results showed that the reaction was a stepwise hydrogenation process and the first H_2 was added to the C1 = C10 double bond in the hydrogenation.
基金financially supported by the Key Program of the Chinese Academy of Science(grant no.KGZD-EW-T08)the National Basic Research Program of China(973 Program,2012CB215500)the"Strategic Priority Research Program"of the Chinese Academy of Sciences(grant no.XDA09030104)
文摘Carbon supported gold-iridium composite(Au Ir/C) was synthesized by a facile one-step process and was investigated as the bifunctional catalyst for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The physical properties of the Au Ir/C composite were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). Although the Au and Ir in the Au Ir/C did not form alloy, it is clear that the introduction of Ir decreases the average Au particle size to 4.2 nm compared to that in the Au/C(10.1 nm). By systematical analysis on chemical state of metal surface via XPS and the electrochemical results, it was found that the Au surface for the Au/C can be activated by potential cycling from 0.12 V to 1.72 V, resulting in the increased surface roughness of Au,thus improving the ORR activity. By the same potential cycling, the Ir surface of the Ir/C was irreversibly oxidized, leading to degraded ORR activity but uninfluenced OER activity. For the Au Ir/C, Ir protects Au against being oxidized due to the lower electronegativity of Ir. Combining the advantages of Au and Ir in catalyzing ORR and OER, the Au Ir/C catalyst displays an enhanced catalytic activity to the ORR and a comparable OER activity. In the 50-cycle accelerated aging test for the ORR and OER, the Au Ir/C displayed a satisfied stability, suggesting that the Au Ir/C catalyst is a potential bifunctional catalyst for the oxygen electrode.
基金supported by the National Natural Science Foundation of China(21421001 , 21573115)the 111 project (B12015)+1 种基金the Fundamental Research Funds for the Central Universities(63185015)the Foundation of State Key Laboratory of Highefficiency Utilization of Coal and Green Chemical Engineering (2017-K13)
文摘Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising catalysts for electrocatalytic reactions due to the earth-abundance and Pt-resembled electrical properties. In this work, taking the advantage of the interaction between the basic groups of the Mo(VI)-melamine polymer and the acidic groups on the surface of the oxidized carbon nanotubes(CNTs), N-doped CNTs supported Mo2C nanoparticles(Mo2C/NCNT) are prepared, which exhibit outstanding electrocatalytic activity and durability for both the hydrogen evolution and oxygen reduction reactions. The impressive performance of Mo2C/NCNT can be attributed to the small size of Mo2C particles, the large exposure ratio of surface sites and the presence of N-doped CNTs. This work enlarges the multi-field applications of molybdenum carbide-base materials as promising non-precious metal electrocatalysts, which is of great significance for sustainable energy-related technologies.
文摘Wittig reactions of benzaldehydes, alkanals, and cycloalkanals as well as of acetophenones are carried out with alkoxycarbonyl methylidenetriphenylphosphoranes in 10 w% aqueous NaOH, where the cinnamates and alkenoates produced are hydrolysed in situ and the corresponding acids are obtained after mostly simple extractive work-up, often without employing organic solvents. Under the same conditions, benzaldehydes are reacted with alkoxycarbonyl bromomethy-lidenephosphorane to produce 3-arylprop-2-ynoic acids (arylpropiolic acids).
基金supported by the National Natural Science Foundation of China (Nos. 21676106 and 21576101)Science and Technology Program of Guangzhou (201704030065)+1 种基金Science and Technology Program of Guangdong (2017A050506015)the Fundamental Research Funds for the Central Universities
文摘Polymer electrolyte membrane fuel cells(PEMFCs), as an energy conversion technology, have attracted extensive attention due to their high conversion efficiency, low emission, high energy density,and fast fuel charging [1,2]. Pt-based catalysts have been acknowledged to be the most effective catalyst for the oxygen reduction reaction(ORR) [3–5]. However, both the source scarcity and high cost of Pt severely hinder the commercial application of the PEMFCs [1,6,7].
基金V. ACKN0WLEDGMENT This work was supported by the Chinese Academy of Sciences, the Ministry of Science and Technology of China, and the National Natural Science Foundation of China.
文摘有 trans-1,3-butadiene 的 F 原子反应的理论研究在 CCSD (T)/6-311G 被执行(d, p )/B3LYP/6-311G (d, p ) 层次。为所有反应物,产品和转变状态的精力和结构是坚定的。包含建筑群 CH <SUB>2</SUB 的形成的二条反应小径 > CHCHFCH <SUB>2</SUB> 和 CH <SUB>2</SUB > CHCHCH <SUB>2</SUB > F 在这反应被发现。理论结果建议在以前的穿过的横梁实验观察的 H 原子隧道经由这二条长寿复杂形成小径多半发生。为复杂 CH <SUB>2</SUB > CHCHFCH <SUB>2</SUB> 小径,另一条反应隧道(C <SUB>2</SUB > H <SUB>3</SUB>+C<SUB>2</SUB > H <SUB>3</SUB > F ) 也是可存取的。C <SUB>2</SUB 的相对重要性 > H <SUB>3</SUB>+C<SUB>2</SUB > H <SUB>3</SUB > 经由一样的反应小径的 F 隧道对 H 形成隧道也被估计了,建议它将是 di ????