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1.
Three silica gel sample systems, modified with 3-amino-propyltriethoxy silane (APTS), were prepared by sequentially sampling
the reaction mixture at various time intervals. The concentrations of 3-aminopropylsilyl groups (APS) bound on the silica
surface were determined by elemental analysis. For the same sample systems, 29Si NMR intensities of an (–O)4Si species belonging only to the silica gel particles and corrected by a cross-polarization correction factor were also measured.
Both the APS-concentrations and the correc-ted 29Si NMR intensities depended upon reaction time, reflecting the rate of the APTS–silica gel reaction. Kinetic analysis of these
data was made by use of the Gauss–Newton method, and the overall reaction was found to consist of three reaction processes
(an initial fast reaction, a slower second reaction and a much slower third reaction). In particular, the conversion of (–O)3SiOH to (–O)4Si is predominant in the second reaction process and the pore size of a silica gel particle affects the reaction mechanism.
Received: 1 November 1996 Accepted: 24 January 1997 相似文献
2.
V. P. Morgalyuk P. V. Petrovskii K. A. Lysenko E. E. Nifant’ev 《Russian Journal of General Chemistry》2010,80(1):100-105
Stoichiometric relations of initial compounds and reaction products in the synthesis of N,N-dialkyl-(diphenylphosphinomethylene)iminium are established; the second reaction product is diphenylphosphinic iodide. Bringing
triphenylphosphine into the reaction increases the N,N-dialkyl(diphenylphosphinomethylene)-iminium yield approximately twice. One of the reaction intermediates is shown to be iododiphenylphosphine.
The reaction can be regarded as disproportionation. 相似文献
3.
The oxime-blocking reaction of several aliphatic isocyanates, such as 1,6-Hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane-4,4′-diisocyanate (H12MDI), is investigated. The reaction is carried on in various solvents that are divided into two categories: aromatic solvents and oxygen-contained solvents. In situ FT-IR is used to monitor the reaction and show the large difference of solvent and the structure of isocyanate. Kinetic studies indicate that the reaction rate appears faster in aromatic solvents although the polarity of aromatic solvents is lower. Then, thermodynamic parameters of the blocking reaction, such as activation energy (Ea), enthalpy (ΔH*) and entropy (ΔS*), are determined from the Arrhenius and Eyring equations. It is found that activation energy in aromatic solvents is higher, but the reaction rate is much faster, all of which are discussed corresponding to the reaction mechanism. 相似文献
4.
Hikmat S. Hilal 《Microchemical Journal》1986,33(3)
Octacarbonyldicobalt(O) has been used to catalyze the reaction of R3SiH (R = Et and EtO) with R′OH (R′ = Me, Et, n-Pr, i-Pr, and t-Bu). The reaction of MeOH with (EtO)3SiH, in toluene at 27 °C, was first-order with respect to the catalyst, to the silane, and to the alcohol. The order of reactivity of the alcohols was MeOH > EtOH > n-PrOH > i-PrOH > t-BuOH, reflecting the steric effect associated with the size of the organic group. Addition of triphenyl phosphine (Ph3P) to the reaction mixture slowed down the reaction. The reaction proceeds faster if nonpolar solvents are used, and the rate of the reaction is very sensitive to temperature. 相似文献
5.
A Grignard reaction of reactantA and phenyl magnesium chloride is used to make a pharmaceutical intermediate at the production scale. The elimination of protecting groups onA was proposed as a means to reduce synthesis costs. This new synthesis route, however, had process efficiency and safety issues associated with it: (1) build-up of unreactedA in the reactor, (2) influence ofA's particle size on the reaction rate, (3) the sensitivity of the reaction rate to the reaction temperature and to the (changing) solvent composition, and (4) the highly exothermic nature of the reaction.The Mettler RC1 Reaction Calorimeter was used to quantify the influence of solvent composition, temperature, and particle size on the reaction rate. Results indicated a dramatic effect of solvent composition and reaction temperature on the reaction rate; for example, over a temperature range of just 30°C, the reaction time decreased from more than a day to just a few minutes. At such high reaction rates, the vessel jacket could not remove the reaction heat sufficiently and the internal temperature rose adiabatically.These results were used to make process design and operation recommendations for safe and efficient plant operation with this modified Grignard reaction system.The authors would like to thank the following for their assistance in this work: E. Daugs for preparing the Grignard reagents, K.L. Gonzales for her help in running the experiments and in the subsequent data work-up; P.M. Russell for his assistance in the design of the slurry addition assembly, and K. Chritz and J. Engel for performing the HPLC analyses of the samples. 相似文献
6.
Jun Matsuoka Minoru Numaguchi Satoshi Yoshida Naohiro Soga 《Journal of Sol-Gel Science and Technology》2000,19(1-3):661-664
Heat of reaction of the hydrolysis-polymerization process of tetraethyl orthosilicate with water in acidic condition was investigated to clarify the thermodynamic driving force of sol-gel reactions. Heat of reaction was measured using an isoperibol calorimeter by mixing a dilute tetraethyl orthosilicate (TEOS) ethanolic solution with another solution of water, ethanol, and hydrochloric acid. The temperature change of the reaction cell had been measured more than 24 hours after mixing under the quasi-isothermal condition. Large exothermic reaction (12.9 kJ·mol–1 for 1 mole of TEOS) due to the hydrolysis of TEOS was observed. A slow exothermic reaction followed it, and after that, the sol-gel reaction was changed to a small endothermic one. 相似文献
7.
Mark C. Finzel John Delong Martin C. Hawley 《Journal of polymer science. Part A, Polymer chemistry》1995,33(4):673-689
The bulk phase kinetics of an epoxy (DGEBA) /amine (DDS) thermoset have been studied using DSC, FTIR, and 13C-NMR. In the absence of catalyst, the reaction was found to involve a main exothermic reaction between epoxide and amine hydrogen and a side reaction between tertiary amine formed in the main reaction and epoxide. The main reaction was exothermic while the side reaction had no discernable exotherm. Etherification did not occur to any significant extent. Since only the main reaction is exothermic, DSC was very useful for studying the main reaction kinetics. FTIR was used for determining whether epoxide and amine hydrogen were consumed at different rates as a way of following the side reaction. An IR band previously unused by other investigators was used to monitor the amine hydrogen concentration. NMR confirmed the above mechanism by identifying the formation of a quaternary ammonium ion/alkoxide ion pair as a reaction product of tertiary amine and epoxide. This mechanism has been successfully fit to a rate law valid over the entire extent of reaction. The rate constant for the epoxy/amine addition reaction was found to depend on hydroxide concentration (extent), reaction temperature, and glass transition temperature and included contributions from uncatalyzed and autocatalyzed parts. The side reaction (quaternary ammonium ion formation) formed weak bonds which did not affect the overall system Tg. Both reactions were second order. The rate constants for the main reaction first increase with increasing extent due to autocatalysis by hydroxide before decreasing due to the diffusion limit caused by gelation and vitrification. © 1995 John Wiley & Sons, Inc. 相似文献
8.
Jianing Huang Jean-Pierre Leblanc H. K. Hall 《Journal of polymer science. Part A, Polymer chemistry》1992,30(3):345-354
Model reactions were carried out to simulate the acidolysis process for polyarylate synthesis by using p-tert-butylphenyl acetate (ptBuPhOAc) and benzoic acid in diphenyl ether. p-tert-Butylphenol was formed in the reaction mixture and its concentration stayed constant throughout the reaction. Acetic benzoic anhydride and benzoic anhydride were detected by NMR. Based on this experimental evidence, a mechanism for the acidolysis was proposed involving the mixed anhydride. The kinetics of the acidolysis reaction was studied for this model reaction. The overall reaction order is two and the reaction order with respect to each reactant is one. Second-order reaction rate constants were measured at different reaction conditions (200–250°C). The activation energy (Ea), activation enthalpy (ΔH≠), and activation entropy (ΔS≠) were calculated from these data. The thermodynamic parameters of the acidolysis reaction were also measured for the analogous reaction of p-tert-butylphenyl pivalate (ptBuPhOPiv) and benzoic acid. The kinetics of two other elementary reactions involved in the acidolysis reaction were also studied: p-tert-butylphenol with acetic anhydride or benzoic anhydride, and p-tert-butylphenyl pivalate with benzoic acid. 相似文献
9.
The bimolecular single collision reaction potential energy surface of CN radical with ketene (CH2CO) was investigated by means of B3LYP and QCISD(T) methods. The calculated results indicate that there are three possible channels in the reaction. The first is an attack reaction by the carbon atom of CN at the carbon atom of the methylene of CH2CO to form the intermediate NCCH2CO followed by a rupture reaction of the C-C bond combined with -CO group to the products CH2CN CO. The second is a direct addition reaction between CN and CH2CO to form the intermediate CH2C(O)CN followed by its isomerization into NCCH2CO via a CN-shift reaction, and subsequently, NCCH2CO dissociates into CH2CN CO through a CO-loss reaction. The last is a direct hydrogen abstraction reaction of CH2CO by CN radical. Because of the existence of a 15.44 kJ/mol reaction barrier and higher energy of reaction products, the path can be ruled out as an important channel in the reaction kinetics. The present theoretical computation results, which give an available suggestion on the reaction mechanism, are in good agreement with previous experimental studies. 相似文献
10.
研究了无溶剂条件下纳米Cu2O催化二苯甲烷二氨基甲酸苯酯(MDPC)热分解制备二苯甲烷二异氰酸酯(MDI),考察了纳米Cu2O的制备条件与反应条件对MDPC热分解反应性能的影响.结果表明,水解法制备的纳米Cu2O在Ar中于300℃焙烧2h,其催化性能最佳;最佳的反应条件为Cu2O用量为原料总重的0.06%,反应温度220℃,反应压力0.6kPa,反应时间12min,此时MDPC转化率达到99.8%,MDI选择性86.2%. 相似文献
11.
Seyyed Amir Siadati 《Helvetica chimica acta》2016,99(4):273-280
It is a well‐known fact that by changing the 1,3‐dipolar cycloaddition (1,3‐DC) reaction mechanism from concerted to stepwise, the stereospecificity is lost; since in synthesizing the required heterocyclic molecules that reaction is a requisite, it is important to study the concertedness of that reaction. Several papers on this subject have already stated that the existence of electron withdrawing groups (EWG) or electron donor groups (EDG) on dipole or dipolarophile leads to a high‐energy differentiation between the dipole HOMO and dipolarophile LUMO (or vice versa) as well as the emergence of an intermediate in the reaction pathway. This paper seeks answering the question of when an EWG on dipole and an EDG on dipolarophile could be a factor in making the reaction mechanism stepwise, and does repositioning of functional groups in replacing dipole and dipolarophile switches the reaction mechanism from stepwise into concerted or vice versa? 相似文献
12.
M. Jabłoński 《Journal of Thermal Analysis and Calorimetry》2008,93(3):717-720
The reaction of sulphuric acid with titanium raw materials runs violently with simultaneous emission of gases. Such run of
reaction creates danger of explosion. This process is very complicated from the reason of complexity of reactions and variety
of compounds in reaction mixture. To determine safe conditions of reaction with high efficiency, it is necessary to investigate
phase composition products of reaction.
Products of reaction were investigated by using X-ray diffraction. However reaction products show high amorphy and this is
the reason of difficulties to determine all phases. For this reason also was used additional method — ‘drop’ calorimeter.
This method is used for determination of average specific heat of liquid or solid samples. In this case, this method was used
for verification of phase composition of products of reaction.
On the basis of investigation the phase composition of reaction product is following: titanyl sulfate, iron(III) sulfate,
monohydrated iron(II) sulfate, magnesium sulfate and unreacted remainders of ilmenite and magnesium silicate. 相似文献
13.
CCl2与CH2O插入反应机理及热力学与动力学特性的理论研究 总被引:3,自引:0,他引:3
采用密度泛函B3LYP/6-311G*和高级电子相关耦合簇[CCSD(T)/6-311G*]方法计算研究了CCl2与CH2O的插入反应机理, 全参数优化了反应势能面各驻点的几何构型, 用内禀反应坐标(IRC)和频率分析方法, 对过渡态进行了验证. 研究结果表明: 反应(1)是单重态二氯卡宾与甲醛插入反应的主反应通道. 该反应由两步组成: (i)两反应物首先经一无能垒的放热反应, 放出9.73 kJ•mol-1的热量, 生成一中间体IM1, (ii)中间体IM1经一过渡态TS1, 发生H的转移, 生成产物P1, 其势垒为47.32 kJ•mol-1. 用RRKM-TST理论计算了300~1900 K温度范围内反应(1)的压力效应. 用经Wigner校正的Eyring过渡态理论研究了不同温度下该反应的热力学和动力学性质. 从热力学和动力学角度综合分析, 在高压限101325 Pa下, 该反应进行的适宜温度范围为400~1800 K, 如此, 反应既有较大的自发趋势和平衡常数, 又具有较快的反应速率. 相似文献
14.
Optimization of alkaline transesterification of soybean oil and castor oil for biodiesel production 总被引:3,自引:0,他引:3
Débora de Oliveira Marco Di Luccio Carina Faccio Clarissa Dalla Rosa João Paulo Bender Nádia Lipke Cristiana Amroginski Cláudio Dariva José Vladimir de Oliveira 《Applied biochemistry and biotechnology》2005,122(1-3):553-560
This article reports experimental data on the production of fatty acid ethyl esters from refined and degummed soybean oil
and castor oil using NaOH as catalyst. The variables investigated were temperature (30–70°C), reaction time (1–3 h), catalyst
concentration (0.5–1.5 w/wt%), and oil-to-ethanol molar ratio (1:3–1:9). The effects of process variables on the reaction
conversion as well as the optimum experimental conditions are presented. The results show that conversions >95% were achieved
for all systems investigated. In general, an increase in reaction temperature, reaction time, and in oil-to-ethanol molar
ratio led to an enhancement in reaction conversion, whereas an opposite trend was verified with respect to catalyst concentration. 相似文献
15.
The Diels-Alder reaction of maldoxin with an isopropenylallene at 60-75 °C afforded an adduct closely related to chloropestolide A (24%) and a second adduct (0-11%) that underwent an ene reaction to generate the chloropupukeanolide D (11-22%) skeleton. The Diels-Alder reaction occurred with good selectively (>5:1) from a single face of maldoxin under much milder conditions than previously reported for the analogous dimethoxycyclohexadienone. Furthermore, the ene reaction took place under mild conditions, whereas the analogous Diels-Alder adduct from the dimethoxycyclohexadienone did not undergo an ene reaction. 相似文献
16.
F. Langmaier P. Mokrejs K. Kolomazník M. Mládek R. Karnas 《Journal of Thermal Analysis and Calorimetry》2007,88(3):857-862
Differential scanning calorimetry was employed to investigate the reaction of diglycidyl ethers of bisphenol A (DGEBA) of
mean molecular mass 348–480 Da, with collagen hydrolysate of chrome-tanned leather waste in a solvent-free environment. The
reaction leads to biodegradable polymers that might facilitate recycling of plastic parts in products of the automotive and/or
aeronautics industry provided with protective films on this basis. The reaction proceeds in a temperature interval of 205–220°C,
at temperatures approx. 30–40°C below temperature of thermal degradation of collagen hydrolysate. The found value of reaction
enthalpy, 519.19 J g−1 (= 101.24 kJ mol−1 of epoxide groups) corresponds with currently found enthalpy values of the reaction of oxirane ring with amino groups. Reaction
heat depends on the composition of reaction mixture (or on mass fraction of diglycidyl ethers in the reaction mixture); proving
the dependence of kinetic parameters of the reaction (Arrhenius pre-exponential factor A (min−1) and activation energy E
a (kJ mol−1)) did not succeed. Obtained values of kinetic parameters are on a level corresponding to the assumption that reaction kinetics
is determined by diffusion. 相似文献
17.
Suresh Babu Meruva A. Raghunadh N. Anil Kumar U. K. Syam Kumar R. Vasu Dev P. K. Dubey 《Journal of heterocyclic chemistry》2011,48(3):540-548
A variety of 5‐aryl‐(20S)‐camptothecin derivatives were synthesized by the reaction of 5‐hydroxy‐(20S)‐camptothecin with aromatic hydrocarbons under Friedel‐Craft reaction conditions in moderate to good yield as diastereomeric pairs. The methodology was then extended for the synthesis of 5‐amido‐(20S)‐camptothecin derivatives by reacting 5‐hydroxy‐(20S)‐camptothecin with alkyl and aryl nitriles under Ritter type reaction conditions. The reaction is presumed to proceed through an iminium ion intermediate under Friedel Craft and Ritter type reaction condition, which is further trapped by nucleophile present in the reaction medium. J. Heterocyclic Chem., 00 , 00 (2011). 相似文献
18.
The oxidation of serine (HORCO2H) by acid permanganate was investigated both in the absence and presence of sodium dodecyl sulfate (SDS). It has been observed that the presence of surfactant enhanced the reaction rate. The reaction is first order with respect to [Serine] and [MnO4?]. The reaction is retarded by the hydrogen ion in the absence of SDS but catalyzed in the presence of SDS. The overall rate expression for the reduction of Mn(VII) may be written as In the presence of SDS of the rate law is The reaction appears to involve a parallel consecutive reaction mechanism in which Mn(IV) appears as the reaction intermediate. ??′4f signifies the rate constant for the reaction path leading to the formation of Mn(IV) from Mn(VII) as reaction intermediate, whereas ??′2f signifies the rate constant for the reaction path leading to the reduction of Mn(VII) to Mn(II) without prior formation of Mn(IV). A mechanism satisfying the various kinetic parameters has been proposed. 相似文献
19.
The potential energy surface(PES) for the reaction of Cl atom with HCOOH is predicted using ab initio molecular orbital calculation methods at UQCIDS(T,full)6-311 G(3df,2p)//UMP2(full)/6-311 G(d,P) level of theory with zero-point vibrational energy (ZPVE) correction.The calculated results show that the reaction mechanism of Cl atom with formic acid is a C-site hydrogen abstraction reaction from cis-HOC(H)O molecule by Cl atom with a 3.73kJ/mol reaction barrier height,leading to the formation of cis-HOCO radical which will reacts with Cl atom or other molecules in such a reaction system.Because the reaction barrier height of O-site hydrogen abstraction reaction from cis-HOC(H)O molecule by Cl atom which leads to the formation of HCO2 radical is 67.95kJ/mol,it is a secondary reaction channel in experiment,This is in good agreement with the prediction based on the previous experiments. 相似文献
20.
Junji Mizukado Yasuhisa Matsukawa Heng-dao Quan Masanori Tamura Akira Sekiya 《Journal of fluorine chemistry》2005,126(3):365-369
ROCHF2-type fluorinated ethers were synthesized by the reaction of hexafluoropropene oxide (HFPO) with alcohol or phenol. In this reaction, although the insertion reaction of difluorocarbene to OH bond and the nucleophilic attack of alcohol or phenol to HFPO were competition, the insertion reaction proceeded predominantly to give fluorinated ether in the case of low nucleophilic alcohol or phenol. In addition, high reaction pressure is advantageous to the selectivity of the fluorinated ethers in the reaction of HFPO with (CF3)2CHOH or C6F5OH. 相似文献