共查询到20条相似文献,搜索用时 31 毫秒
1.
Substituent effects on the proton dissociation of protonated aniline derivatives upon femtosecond laser pulse excitation are investigated for m- and p-cyanoanilines and m- and p-methoxyanilines in aqueous solution. The cyano substitution at the meta-position increases the rate significantly (kdis=3.7 × 1011 s−1) compared to aniline (kdis=1.3 × 1010 s−1), while the methoxy substitution reduces the rate remarkably. Either substituent at the para-position shows only slight influences on the rate. The strong dependences of the kdis value on the substituent and the substituted position are reasonably explained on the basis of the free energy change. 相似文献
2.
K. Joseph Antony Raj M.S. Meenakshi V.R. Vijayaraghavan 《Journal of molecular catalysis. A, Chemical》2007,270(1-2):195-200
The vapour and liquid phase ethylation of ethylbenzene was performed over AlPO4-5 and its substituted counter parts. The results obtained for vapour phase reactions have shown a higher catalytic activity at 350 and 400 °C. The catalysts, however, exhibited a faster deactivation rate. The results obtained for liquid phase reaction have shown a higher selectivity for para-diethylbenzene (84.4%) than the vapour phase reaction (41.5%). MnAPO-5 was found to be active up to 240 h for the liquid phase reaction. para-Diethylbenzene, meta-diethylbenzene and polyalkylbenzene were the major products obtained for ethylation of ethylbenzene. When ethylbenzene passed over MnAPO-5 yielded products, such as benzaldehyde, acetophenone, styrene and 2,3-diphenylbutane. This showed a preference for oxidation rather than disproportionation followed by alkylation. Notwithstanding the better acid characteristics of ZSM-5, MnAPO-5 could be a better choice for this class of reaction essentially due to its higher para selectivity. 相似文献
3.
《Tetrahedron》1963,19(12):2199-2207
2,5 Diaryloxazoles, with the 2-, and 5-aryl groups, substituted in the para position by halo, methyl, methoxy or nitro groups were obtained by the Friedel-Crafts reaction of p-substituted hippuric acid azlactones with benzene, or the hippuric acid azlactone with halobenzenes, toluene, and anisole, followed by treatment with phosphorus oxychloride. Grignard and Ullmann reactions of p-halo-substituted 2,5-diaryloxazoles are described. Absorption spectra of these compounds are discussed and the pronounced bathochromic effect of coupled donor and acceptor groups in both para positions is accounted for by a simple MO treatment. 相似文献
4.
The rate constants, kCR, of ortho- into para-positronium (o-Ps→p-Ps) spin conversion reactions, CR, caused by the high-spin [CoIIsep]2+, [CoIIdinosar]2+ and [CoIIdiamsar]2+ macrocyclic complexes and also by high-spin [CoII sen]2+ tripod complex were measured at several temperatures. The delocalizations, β, of CoII unpaired electrons, promoted by the mentioned ligands, were determined by using the previously established correlations between kCR and the electron delocalization β of unpaired metal electrons. β is given by the ratio between the Racah inter-electronic repulsion parameters of complexes, B, and that of the free ions, B0. The β values are compared with those of the CoII complexes with en (1,2-ethanediamine), pn (1,2 propanediamine) and dien (2,2′ diamino diethylamine) ligands. The kCR rate constants are also compared with those of the Ps oxidation reactions, OR, promoted by the corresponding CoIII complexes. It is concluded that, unlike OR's, the CR's do not occur by formation of hepta-coordinate adducts with Ps atoms. 相似文献
5.
The vapour pressures of n-octane have been measured using comparative ebulliometry with water as the reference fluid. The results cover the temperature and pressure range (323.2 K, 6.7 kPa) to (563.3 K, 2301.7 kPa) and have been described by a Wagner style equation with a fractional standard deviation of 3.3×10−5 in the vapour pressure. The critical pressure pc was treated as an adjustable parameter and the value of pc=2482 kPa was obtained using the literature value for the critical temperature. An Antoine equation that describes the results below a pressure of 142 kPa with a standard deviation of 1.4 mK in the condensation temperature has also been obtained. 相似文献
6.
Oxidation of phenol by aqueous alkaline peroxydisulfate to form o− and p-dihydroxybenzenes has been studied. The rate is expressed as: v = k[s2O8=[PhOH], where the k value tends to increase with an increase of the concentration of alkali and a plot of log k vs pH at pH 9·5-10 is a straight line with a slope of ca unity. The effects of ionic strength, concentration of alkali and temperature on the o/p ratio has been determined. In view of these facts a probable mechanism involving a nucleophilic attack of a C atom of phenoxide ion on the peroxide oxygen of the peroxydisulfate ion has been postulated and discussed. 相似文献
7.
Six varieties of liquid-crystalline side-chain polymers, poly (cholesteryl ω-(methacryloyloxy)alkanoates) (p-ChMO-n, n = 1,2,3,4,5,7, the carbon number of the alkyl chain), were studied by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS). On and after the first cooling run from the isotropic state, these polymethacrylates gave the same smectic phase. However, on the first heating run for virgin samples, unique phenomena were observed, similar to those frequently observed on the first heating run for thermotropic liquidcrystalline polymers. The thermal properties of the first heating run for these six polymers showed different tendencies between pChMO-n (n-1-3) and pChMO-n (4-7). Although the DSC curve of pChMO-n (n = 4, 5 and 7) exhibited the melting and clearing points on the first heating run, the DSC curve of pChMO-n (n = 1,2 and 3) exhibited an exothermal peak between the glass transition and the clearing point on the first heating run. This difference, probably due to the difference in the spacer length of these polymers, was investigated quantitatively by small-angle X-ray scattering by which the micro-change of the packing structure of the side chains of the polymers was traced. 相似文献
8.
F. Rodante S. Vecchio G. Catalani M. Guidotti 《Journal of Thermal Analysis and Calorimetry》2000,60(2):605-622
The thermal behaviour of some commercial pesticides was studied by simultaneous TG/DSC measurements. Kinetic parameters, related
to solid-gas phase transition processes, were also carried out by using dynamic TG technique.
The kinetics were analysed by using Arrhenius, Satava and Harcourt-Esson equations. The choice of the mathematical expression
to insert in these equations was influenced by the shape of the TG plot and other thermal analysis signals. The compounds
studied undergo a fusion process followed by a single vaporization process. The latter is well represented by a diffusive
process (D1, D2 or D3). The variation of the activation energy values within the range of temperature where the vaporization processes occur was
calculated. The enthalpy values of vaporization were also evaluated by using the Clausius-Clapeyron equation.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
9.
The rate constants, kCR, of conversion reactions, CR, of ortho- into para-positronium atoms promoted by 3d paramagnetic complexes of VII, CrII, CrIII, MnII, CoII and NiII ions are linearly correlated with the electron delocalization β caused by the ligands. β's may be evaluated by means of the empirical equation β=1−th, where t and h are constants characteristic of the ion and ligands, respectively. The determination of the unknown t(FeII) value is here described. It was derived by means of the rate constants of the CR caused by some FeII complexes. It was found that t(FeII)=0.14±0.01. A relationship between t and the oxidation number of the metal ions is suggested. 相似文献
10.
Kinetic experiments have been carried out on the reactions of isoquinoline N-oxide with p-toluenesulfonyl and other substituted benzenesulfonyl chlorides, varying solvent and salt compositions. The rate was correlated by the second-order equation, i.e., v = [N → O] × [ArSO2Cl], and was found to be accelerated in polar media. The addition of chloride ion was found to increase the rate considerably, while the rates of the over-all reaction became greater with arenesulfonyl chlorides bearing stronger electron-withdrawing substituents ( = +2·0). By the use of 1-deuterated isoquinoline N-oxide a small kinetic isotope effect (kH/kD = 1·2) was observed for this reaction. Based on these kinetic observations the rate-determining step of this reaction is considered to be the cleavage of N---O bond. Meanwhile, from the 18O-tracer experiments in several solvents using uniformly 18O-labelled p-toluenesulfonyl or p-bromobenzenesulfonyl chloride the migration of arenesulfonate was found to proceed mainly via oxygen-bridged ion pair pathway. 相似文献
11.
A Sherwood correlation (mass transfer correlation) pertinent to natural organic matter–nanofiltration (NOM–NF) systems was established through the determination of the mass transfer coefficient (k) based on a combined film/thermodynamic approach, under laminar flow conditions. In this study, the NOM transport characteristics inside a NF membrane were quantitatively demonstrated through the pore Peclet number (Pe) calculated from experimental data. Transport experiments were performed, using a plate-and-frame crossflow test unit, at various feed flow rates, with a thin-channel type test cell that could be adjusted to different channel heights. The transport experimental results, with Suwannee River NOM (SRNOM), show that the transport of the SRNOM through the NF membrane (denoted as ESNA, MWCO of 200–250) was dominated by diffusion, which was further confirmed by the determined pore Pe (Pe < 1.0). The Sherwood correlation established for the SRNOM and NF membrane under ambient conditions (neither pH nor ionic strength adjustment) exhibited the standard form: Sh = 0.853Re0.550Sc0.363. The k values calculated by the correlations (kSh) were in good agreement with those determined from the experiments (kexp). However, significant discrepancy between the kSh and kexp was observed with alterations in the feed water chemistry. The kSh value increased with either decreasing pH or increasing ionic strength, as the experimentally determined diffusion coefficient of the SRNOM increased under these condition, whereas, the kexp exhibited opposite trends, due to the decreased water permeation (or suction) rate, increased NOM transmission and decreased electrostatic repulsion. The k values for other source water NOM (but with the same membrane) were also estimated by the Sherwood correlation coupled with diffusion cell tests. The discrepancy between the kSh and kexp values was less than 20%, and the discrepancy decreased with increased feed flow rate. 相似文献
12.
Three new ferrocene-based compounds were prepared which formed liquid crystalline phases in the melt, as follows: 1,1'-bis(p-heptoxyphenyl)ferrocene dicar-boxylate, I; 1,1'-bis(p-decycloxyphenyl)ferrocene dicarboxylate, III; and 1-(p-decyloxyphenyl)-1'-(p-hydroxyphenyl)ferrocene dicarboxylate, IV. All three were characterized for their liquid-crystalline properties by polarized light microscopy, DSC and wide-angle X-ray diffraction. 相似文献
13.
Stefano Vecchio 《Structural chemistry》2013,24(6):1821-1827
A rapid estimation of vapor pressure and vaporization enthalpies of some disubstituted benzoic acids (2,4-dihydroxybenzoic acid (2,4-DHBA), 2,6-dihydroxybenzoic acid (2,6-DHBA), 3,4-dihydroxybenzoic acid (3,4-DHBA), 2,4-dinitrobenzoic acid (2,4-DNBA), 3,4-dinitrobenzoic acid (3,4-DNBA), 2,5-dibromobenzoic acid (2,5-DBBA), and 3,5-dibromobenzoic acid (3,5-DBBA)) was made using a simultaneous TG/DSC apparatus operating with aluminum open crucibles under inert atmosphere in both isothermal and non-isothermal mode. No evidence of thermal decomposition (in the form of endo or exothermic effect) was found during each experiment. Vapor pressure was obtained in the range from some tenth to some hundreds of Pa after calibration with benzoic acid. All operative conditions (sample mass, temperature rage, and purge gas flow) were carefully checked in order to obtain reliable results. Internal consistency of the results obtained was checked by comparing the sublimation enthalpy obtained by the sum of the vaporization enthalpies derived by the global NITG and ITG data, the melting enthalpies from DSC adjusted at 298.15 using the molar isobaric heat capacities of both solid and liquid estimated according to a group additivity approach and that obtained from the sublimation enthalpies determined by torsion effusion corrected at 298.15 K using the same approach. Finally, some comments concerning the relationship between energetics and structure (substituent effect) are also reported. 相似文献
14.
Agna Hélia de Oliveira Elisana Afonso de Moura Márcia Ferraz Pinto José Valdilânio Virgulino Procópio Valmir Gomes de Souza Fábio Santos de Souza Rui Oliveira Macêdo 《Journal of Thermal Analysis and Calorimetry》2011,106(3):763-766
This work studied the thermal characterization of the pentoxifylline raw material through thermoanalytical techniques (TG,
DSC, DSC-photovisual) and analysis of degradation products by Pyr-GC/MS. The picture obtained with DSC-photovisual showed
the total vaporization of pentoxifylline at 230.0 °C. The TG dynamical curve presented only one step for the loss of mass
evidencing to be a kinetic process of zero order reaction. The pyrograms obtained for pentoxifylline sample in the solid state
and solution in the temperatures of 250.0, 300.0, and 400.0 °C, showed only one peak identifying the pentoxifylline. 相似文献
15.
The structures of ionic liquids (ILs) based on 1-alkyl-3-methylimidazolium chloride [Cnmim]Cl (n = 2, 4, 6), (1-ethyl-3-methylimidazolium chloride [C2mim]Cl, 1-butyl-3-methylimidazolium chloride [C4mim]Cl, and 1-hexyl-3-methylimidazolium chloride [C6mim]Cl) were elucidated by 1 H NMR and 13 C NMR experiments. The vaporization characteristics of these ILs were studied by thermogravimetric analysis. Dynamic and isothermal thermogravimetric experiments were conducted in this study. The purpose of the dynamic experiments was to determine the initial decomposition temperature of the experimental sample and the temperature range for the isothermal thermogravimetric experiments. The purpose of the isothermal experiments was to record the mass dependence of the sample on time in the experimental temperature range. The Langmuir equation and Clausius-Clapeyron equation were used to fit the experimental data and obtain the vaporization enthalpies of these ILs at the average temperature within the experimental temperature range. However, in order to expand the applicability of the estimated values and to compare them with the literature data, the vaporization enthalpy ΔHvap(Tav) measured at the average temperature was converted into vaporization enthalpy ΔHvap(298) at ambient temperature. The difference between the heat capacities of the ILs in the gaseous and liquid states at constant pressure, ΔlgCpmө proposed by Verevkin, was used in this conversion process. The experimental data for substance density and surface tension at other temperatures were obtained by referring to the literature. In addition, the data for density and surface tension at T = 298.15 K were obtained by applying the extrapolation method to the literature values for other temperatures. The vaporization enthalpy of the 1-octyl-3-methylimidazolium chloride IL [C8mim]Cl was estimated by using the new vaporization model we had proposed in our previous work and compared with the reference value. The estimated value for [C8mim]Cl was on the same order of magnitude as the reference value. We compared the vaporization enthalpies in the present study with those for the carboxylic acid imidazolium and amino acid imidazolium ILs ([Cnmim]Pro (n = 2-6) and [Cnmim]Thr (n = 2-6), respectively in our previous work. The results revealed that a change in the anion type affects the vaporization enthalpy of the ILs in the order amino acid imidazolium > carboxylic acid imidazolium > halogen imidazolium, when the cation is the same. Considering the structural differences between the three kinds of ILs, the abovementioned order may be related to the intermolecular hydrogen bonds. There were no intermolecular hydrogen bonds in the [Cnmim]Cl (n = 2, 4, 6) ILs studied here. Therefore, the vaporization enthalpy of [Cnmim]Cl (n = 2, 4, 6) was the lowest among the three kinds of ILs considered. 相似文献
16.
The thermal stability in air of 5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin (4-TMPP), 5,10,15,20-tetrakis (3-methoxyphenyl) porphyrin (3-TMPP), and their nickel metallo-complexes (4-TMPP-Ni and 3-TMPP-Ni) has been investigated by thermogravimetry (TG). 4-TMPP and 4-TMPP-Ni exhibit higher thermal stability compared to 3-TMPP and 3-TMPP-Ni. Nickel complexes exhibit a little higher thermal stability than the corresponding porphyrins. The thermal behavior including melting temperature and enthalpy of fusion was determined by differential scanning calorimetry (DSC) and infrared spectra (IR). The activation energies of thermal decompositions of 4-TMPP-Ni and 3-TMPP-Ni were obtained by integral model-free method; the mechanism functions and pre-exponential factors were determined by master plots method. The kinetic models follow the same mechanism function, Avramie-Erofeev equations with integral forms g() = [−ln (l − )]0.278 and g() = [−ln (l − )]0.260, respectively. 相似文献
17.
Jenny Tang Ian Brackenridge Stanley M. Roberts Jean Beecher Andrew J. Willetts 《Tetrahedron》1995,51(48):13217-13238
The use of (R)-methyl para-tolylsulfoxide as a chiral auxiliary in a novel synthesis of a key intermediate en route to mevinic acid-type hypocholestemic agents is described. The synthesis is short and simple consisting of eight steps to yield enantiomerically pure β-silyloxy-δ-lactone. The chiral sulfoxide used in the synthesis was obtained via a straightforward biooxidation of methyl para-tolylsulfide using bakers' yeast (Saccharomyces cerevisiae NCYC 73). The biotransformation involves the use of whole cells and affords the sulfoxide in good yield and with high stereoselectivity. 相似文献
18.
采用CCSD(T)/6-311++G(3df, 2pd)//B3LYP/6-311+G(2df, 2p)双水平计算方法构建了HO2+HS反应体系的单、三重态反应势能面,并对该反应主通道的速率常数进行了研究。研究结果表明,标题反应经历了八条反应通道,其中三重态反应通道R1是标题反应主通道。此通道包含路径Path 1 (R → 3IM1 → 3TS1 → P1(3O2+H2S))和Path 1a (R → 3IM1a → 3TS1a → P1(3O2+H2S))两条路径。利用经典过渡态理论(TST)与变分过渡态理论(CVT)并结合小曲率隧道效应模型(SCT),分别计算了主路径Path 1和Path 1a在200-800 K温度范围内的速率常数kTST、kCVT和kCVT/SCT,在此温度区间内路径Path 1和Path 1a具有负温度系数效应。速率常数计算结果显示,对主路径Path 1和Path 1a而言,变分效应在计算温度段内有一定影响,与此同时量子力学隧道效应在低温段有显著影响。路径Path 1和Path 1a的CVT/SCT速率常数的三参数表达式分别为k1CVT/SCT(200-800 K) = 1.54×10-5T-2.70exp(1154/T) cm3 ·molecule-1·s-1和k1aCVT/SCT(200-800 K) = 5.82×10-8T-1.84exp(1388/T) cm3·molecule-1·s-1。 相似文献
19.
Jia Qing-Zhu Ma Pei-Sheng Zhou Huan Xia Shu-Qian Wang Qiang Qiao Yan 《Fluid Phase Equilibria》2006,250(1-2):165-172
Using a laser monitoring observation technique, solubilities of o-nitro-benzoic acid, p-hydro-benzoic acid, p-methyl-benzoic acid and m-methyl-benzoic acid in water have been measured in the temperature range 290.15–323.15 K. The experimental data are regressed with the Wilson equation and the λH equation. The experimental results show that solubilities of these compounds in the range of 10−4–10−5 mole fraction in water, increase significantly with temperature. Except for o-nitro-benzoic acid, the solubility data are described adequately with the Wilson equation. The λH equation gives good agreement with all experimental data. The results indicate that the molecular structure and interactions affect the solubilities significantly. 相似文献
20.
《Liquid crystals》2001,28(9):1321-1329
A series of intermolecular hydrogen bonding complexes, 2,2'-bipyridine: p- n-alkoxybenzoic acids (BP : nABA) was isolated from liquid crystalline p-n-alkoxybenzoic acids (nABA) (where n represents alkoxy carbon numbers, 3 to 10 and 12) and a non-mesogen, 2,2'-bipyridine (BP). The thermal and phase behaviour of these complexes was studied by thermal microscopy and differential scanning calorimetry (DSC). These studies revealed the induction of tilted smectic F and crystal G phases. The structural elucidation pertaining to the formation of intermolecular hydrogen bonding was carried out by a detailed IR spectral investigation. Comparative crystallization kinectic studies using DSC, performed on two representative compounds, showed different forms of the crystallization process. The magnitudes of the Avrami exponent n suggests two different mechanisms operate for individual members leading to sporadic three-dimensional growth. Nevertheless, an overall unique mechanism is predicted to operate at each crystallization temperature investigated, while the Avrami constant b shows a temperature dependence suggesting a strong influence of alkoxy terminal groups on the rates of nucleation. 相似文献