热分析动力学与热动力学

正热分析动力学与热动力学是用热分析和量热技术研究某些物理变化或化学反应动力学的分支学科,是目前热化学最活跃的研究领域之一。热分析动力学主要研究反应过程的活化能和机理函数,热动力学则是在量热学、化学热力学和化学动力学的基础上,通过高精度、自动化和连续式的微     

溴的药物动力学及药效动力学

本世纪以来,含溴药物及其临床应用的研究得到了空前的发展,在2001-2010年十年间,有关含溴药物的药物动力学和药效动力学中文文献数亦占相关文献总数的80％左右,目前研究的药物主要集中于呼吸系统用药和神经肌肉阻断药.综述了溴化物的生物半衰期、8种药物的药物动力学和5种药物的药效动力学研究概况.     

加聚反应微观动力学

聚合反应微观动力学发展了一些成功的理论。图形分析方法具有严格、简明、普适的特点。化学动力学与物理扩散过程的结合提出了一些新问题,将有力地推动高分子化学和聚合反应工程学的发展。     

聚合物结晶动力学

本文介绍了聚合物等温及非等温结晶动力学过程的理论和实验方法，对影响动力学过程的一些因素进行了讨论。     

乳酸缩聚反应动力学

乳酸直接缩聚制备聚乳酸的反应在１２４℃无外加催化剂时，在反应程度１０％～６０％的范围内符合３级反应，其动力学方程式为：ｌＩ］３；在１２０℃，１％（ｗｔ）强酸性离子交换树脂作催化剂时，在反应程度１０％～５０％的范围内符合２级反应，其动力学方程式为：＝Ｉ０１ｃｏｏｎｊ＝。     

动力学定量分析法

近年来,动力学定量分析法用于痕迹量的分析有所进展。由于这种方法灵敏度和准确度都很高,适用于相当广泛的分析对象;分析     

镉卟啉生成反应动力学及动力学盐效应研究

对四－间甲基－苯基卟啉Ｈ２Ｔ（ｍ－ＣＨ３）ＰＰ与Ｃｄ（Ⅱ）离子在丙酮中生成反应进行了研究。提出了合理的反应机理，探讨了温度对反应速率的影响规律，并发现较高离子强度对反应速率的影响呈负盐效应，根据Ｄｅｂｙｅ－Ｈｕｅｃｋｅｌ理论和实验结果，得到了反应的速率常数与离子强度间的定量关系式。     

动力学分析法概论

本文概要论述了动力学分析法的特点、分类及其意义,并对有关基础知识进行了讨论。     

化学反应动力学研究法

由完全非线性函数ｆ（ｔ）＝Ａ＋Ｂｅ＾－ｋ１ｔ＋Ｃｅ＾－ｋ２ｔ经变换得到自函数递推方程，根据回归分析理论，建立了一种化学反应动力学研究法－－自函数回归法，应用该法在２５℃水溶液中研究了乙酸乙酯和丁酸乙酯的皂化反应的动力学常数。     

Co2+与BPPT络合反应动力学及动力学光谱法测定钴

Thiosemicarbazones and phenylthiosemicarbazones are in- teresting ligands because of their ability to form highly stable and intensely colored complexes, which is attributed to the for- mation of bond between sulfur and hydrazino nitrogen atoms, and these…     

Study of kinetics of complexation reaction of Co with 2-benzoylpyridine-4-phenyl-3-thiosemicarbazone and kinetic-spectrophotometric determination of cobalt

Kinetics of the complexation reaction of Co²⁺ with 2-benzoylpyridine-4-phenyl-3-thiosemicarbazone (BPPT) was spectrophotometrically examined at 421 nm. The ligand that was developed for a simple kinetic-spectrophotometric determination of Co²⁺ was based on 1:2 complex formation between Co²⁺ and BPPT. The complexation reaction was carried out in ethanol-water medium at 25 °C. Kinetic and activation parameters of the complexation reaction were calculated, and the rate equation and the reaction mechanism were proposed. The calibration graph is linear in the concentration range of 0.10−2.91 mg·L⁻¹ for the tangent method. The species that caused interference were investigated.     

The Influence of Temperature on the Adsorption of Cadmium(II) and Cobalt(II) on Goethite

The adsorption of Cd(II) and Co(II) onto goethite was measured at five temperatures between 10 and 70 degrees C. For both cations the amount adsorbed at any given pH increased as the temperature was increased. Cd(II) adsorbed at a slightly lower pH at each temperature than Co(II). Adsorption isotherms at pH 7.00 for Cd(II) could be fitted closely by a simple Langmuir model, but a two-site Langmuir model was needed for Co(II). Potentiometric titrations of goethite suspensions in the presence and absence of added cation could be modeled closely by a constant-capacitance surface complexation model that assumed the adsorption reactions M2+ + SOH ⇋ SOM+ + H+ and M2+ + SOH + H2O ⇋ SOMOH + 2H+, where M represents Cd or Co. This model also fitted the experimental data from the adsorption edge and adsorption isotherm experiments. Thermodynamic parameters estimated from both Langmuir and surface complexation models showed that the adsorption of both metals was endothermic. Values obtained for the adsorption enthalpies from both modeling schemes were similar for both cations. Estimates of the adsorption entropies were model-dependent: Langmuir parameters yielded positive entropies, while some of the surface complexation parameters generated negative adsorption entropies. Copyright 1999 Academic Press.     

Determination of trace amounts of cobalt using 1-(5-bromo-2-pyridylazo)-2-naphthol-6-sulfonic acid-Cu(II)-Co(II) competitive replacement complexation

The chromophore 1-(5-bromo-2-pyridylazo)-2-naphthol-6-sulfonic acid (BPANS) has been used to sensitively complex Cu(II) and Co(II) in aqueous solution at pH 9.43. The spectral correction technique was applied to characterize the complexes, and results showed that both Cu(BPANS)2 and Co(BPANS)2 were formed. Trace Co2+ replaced the Cu(II) in the Cu-BPANS complex, so the competitive replacement complexation (CRC) was used to improve the analytical selectivity. A novel light-absorption ratio variation approach (LARVA) was described as one of the most sensitive methods. The combination of CRC and LARVA was applied to the quantitative detection of Co(II) at the ng/mL level. The limit of detection was only 2.0 ng/mL Co, and the analysis of water samples demonstrated satisfactory results.     

Ferrocene-cyclam: a redox-active macrocycle for the complexation of transition metal ions and a study on the influence of the relative permittivity on the coulombic interaction between metal cations

The reaction of 1,1'-ferrocene-bis(methylenepyridinium) salt with 1,4,8,11-tetraazacyclotetradecane-5,12-dione, followed by LiAlH4 reduction results in the formation of FcCyclam. Metal complexes of FcCyclam with M2+ = Co2+, Ni2+, Cu2+, and Zn2+ were synthesized from FcCyclam and the respective metal triflates. The complexation of Cu2+ and FcCyclam in CH3CN is preceeded by a rapid electron transfer, followed by a slower complex formation reaction and a reverse electron transfer. The protonation constants of FcCyclam and the stability constants for the Cu2+ complex of FcCyclam (logK = 9.26(4) for the formation of the [Cu(FcCyclam)]2+ complex) were determined in 1,4-dioxane/water 70:30 v/v, 0.1 moldm(-3), KNO3, 25 degrees C. By using FcCyclam one can selectively sense the presence of Cu2+ ions in the presence of Ni2+, Zn2+, Cd2+, Hg2+, and Pb2+ with a very large deltaE approximately 200 mV, depending on pH. The X-ray crystal structures of FcCyclam and of complexes with Co2+, Ni2+, Cu2+, and Zn2+ were determined and Fe-M2+ distances obtained: Fe-Co2+ 395.9, Fe-Ni2+ 385.4, Fe-Cu2+ 377.7, and Fe-Zn2+ 369.0 pm. The redox potential of FcCyclam is influenced in a characteristic manner by the complexation of M2+. A linear correlation of 1/r approximately/= deltaE [r = distance Fe-M2+ from crystal data, deltaE=-E1/2([M(FcCyclam)]2+) - E1/2(FcCyclam)] was found; this is indicative of a mainly Coulomb type interaction between the two metal centers. The nature of the Fe...M2+ interaction was also investigated by determining deltaE in several solvents (mixtures) of different dielectric constants epsilon. The expected relation of deltaE approximately/= 1/epsilon was only found at very high values of epsilon. At epsilon < 40 increased ion-pairing appears to reduce the effective positive charge at M2+ leading to progessively smaller values of deltaE with lowered epsilon. The dependence of deltaE and epsilon can be calculated semiquantitatively by combining the Fuoss ion-pairing theory with the Coulomb model.     

钙钛矿型La1+X/2Sr1-x/2Co1-xCuxO3催化CO氧化活性与表征

The catalytic activity and the reactive properties of perovskite-type oxides catalysts La(1+x/2)Sr(1-x/2)Co1-xCuxO3 for CO oxidation reaction were investigated. Results showed that the catalytic activity for CO oxidation reached to a maximum when x＝0.4. The temperature for complete CO oxidation under atmospheric and experimental conditions was 168℃. According to the stoicheometry of catalyst, all catalysts were oxygen defect compounds. The active oxygen species on this catalyst was the adsorbed oxygen which was adsorbed on the surface lattice oxygen defect. It was also found that Co4+ existed in the catalysts and the sufrace active oxygen species was caused by the Co4+. It was concluded that CO oxidation reaction on this catalyst was carried out by the valence change between Co3+ and Co4+ which was adjusted by the adsorbed oxygen.     

On-capillary complexation of metal ions with 4-(2-thiazolylazo)resorcinol in capillary electrophoresis

Co(II), Zn(II), Ni(II) and Fe(I) were successfully separated by capillary electrophoresis using pre-capillary and on-capillary complexation with 4-(2-thiazolylazo)resorcinol. The influences of some crucial parameters, including both pre- and on-capillary complexation procedure, were investigated. For on-capillary complexation, the complexing reaction was carried out inside the capillary by mixing the zones of ligand and sample during the electrophoretic migration. Compared with pre-capillary complexation, the method provided 30-fold reduction in detection limits for Co(II), 50-fold reduction for Zn(II), and 100-fold reduction for Ni(II) and Fe(II). It was used for the analysis of a pharmaceutical and tap water sample.     

Complexes of 5,5'-aminoacido-substituted 2,2'-bipyridyl ligands: control of diastereoselectivity with a pH switch and a chloride-responsive combinatorial library

The synthesis and coordination chemistry of a new chiral ligand, 2,2'-bipyridine substituted at the 5 and 5' positions by N-methyl-L-valine methyl ester (5), is presented. The ligand readily forms complexes [M(5)3]2+ where M = Co(II) and Fe(II) in CH3CN, and the complexation reaction is slightly diastereoselective (d.e. =ca. 20%) in favour of the Delta diastereomer. The addition of six equivalents of HCl to these complexes [M(II)(5)3]2+ leads to formation of Delta-[M(II)(5H2)3]8+ with a d.e. of 100%. This high diastereoselectivity can be reversed by the addition of base i.e. the diastereoselectivity can be controlled by the pH. Delta-[Fe(5H2)3]8+ was found to bind chloride ions in CD3OD-CD3CN (6:1) with a binding constant of 260 M(-1). [Co(II)(5)3]2+ can be oxidised to Delta-[Co(III)(5H2)3]9+. Formation constants for both [Co(II)(5)3]2+ and [Co(II)(5H2)3]8+ in acetonitrile were obtained by spectrophotometric titrations. In the former case, the stability constant, log beta3 = 19.5(8), is very similar to that measured for [Co(II)(bipy)3]2+ (log beta3 = 19.3(7)) but this drops significantly when the amine groups of are protonated (log beta3 = 16.5(2)). A dynamic combinatorial library was prepared by mixing three equivalents of, three equivalents of bipy, and two equivalents of Co(II) in CD3CN. The presence of all possible Delta- and Lambda-[Co(II)(5)x(bipy)(3-x)]2+ complexes was inferred from 1H NMR and ES-MS spectra. Addition of protons to this library reduced the number of components by inducing diastereoselectivity, and presence of chloride further simplified the 1H NMR spectrum, indicating that [Cl2 ligand Delta-[Co(II)(5H2)3]]6+ and [Co(II)(bipy)3]2+ were the dominant products.     

Spectrophotometric and conductometric studies of the thermodynamics complexation of Zn2+, Ni2+, Co2+, Pb2+ and Cu2+ ions with 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane ligand in acetonitrile solution

The complexation reaction between 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane ligand (Kryptofix5) and Zn²⁺, Ni²⁺, Co²⁺, Pb²⁺ and Cu²⁺ ions were studied conductometrically in acetonitrile solution. The formation constants of the resulting 1:1 complexes were calculated from the computer fitting of the molar conductance and absorbance measurements in various mole ratios. The enthalpy and entropy changes of the complexation reactions were derived from titration conductometry in acetonitrile at various temperatures. At 25 °C, the stability of the resulting complexes varied in the order Pb²⁺ > Zn²⁺ > Cu²⁺> Co²⁺> Ni²⁺.     

Development of capillary electrophoresis for the determination of metal ions using mixed partial and complete complexation techniques

A new capillary electrophoretic (CE) method was developed for the selective and sensitive determination of common metal ions. The proposed method is based on conventional CE separation of metal cations followed by complete complexation of separated analytes with 1,10-phenanthroline using the zone-passing technique. This approach combines both partial and complete complexation modes and, thus, enables rapid, selective, efficient separation together with sensitive direct UV detection of metal species. The optimal conditions for the separation and derivatization reaction were established by varying type of electrolyte, electrolyte pH, introduction time and concentration of 1,10-phenanthroline. The optimized separations were carried out in 50 mmol l(-1) glycolic acid electrolyte (pH 6.0 with imidazole) using direct UV detection at 254 nm. Five common metal cations (Fe2+, Co2+, Ni2+, Cu2+ and Zn2+) were separated in less than 4 min. The proposed system was applied to the determination of Fe(II) and Zn(II) in snow samples. The recovery tests established for snow samples were within the range 100+/-12%.