丝裂霉素C的酸解动力学研究

我们用高效液相色谱(HPLC)研究了抗生素类抗癌药物丝裂霉素C(MMC)的酸解反应动力学.MMC在酸性介质中水解,生成三种产物.该酸解反应属一级平行反应.本文给出了介质pH值、浓度和温度对酸解速率常数的影响规律.对高效液相色谱分离出来的酸解产物作了红外光谱和吸收光谱研究.还讨论了MMC酸解反应的机理.

磷尾矿酸解动力学研究

以磷尾矿为研究对象,在前期试验获得较佳酸解工艺条件下,考察了反应温度、硫酸质量分数对MgO浸出率的影响。由动力学曲线看出,反应速率常数随温度升高而增大,但增大的程度并不明显,该酸解反应为扩散控制;德罗兹多夫动力学方程1/tln1/1-x-βx/t=k能很好描述该酸解反应;计算出表观活化能Ea=16.033kJ/mol,为固膜扩散控制。

金河磷矿在硫、磷混酸中的溶解动力学

参考二水物湿法磷酸的生产工艺条件，进行了金河磷矿在硫、磷混酸中的酸解动力学研究．考察了矿粉粒度、硫酸浓度及反应温度对酸解过程的影响；选用考虑了自阻化因素的德罗兹多夫方程描述酸解过程的动力学；利用修改后的Gioia酸解模型求得了磷矿酸解过程的有效扩散系数．

硫酸分解开阳磷矿动力学特性研究

采用贵州开阳磷矿，研究了硫酸分解磷矿时的反应温度、磷矿粒度、硫酸浓度、搅拌强度和反应时间等对磷矿分解率的影响。指出过程属于扩散控制，提出了酸解动力学模型为：1-（1-Y）1/3=kt1/5，并检验了模型的正确性。

鹤峰磷矿在硫、磷混酸中的溶解动力学

对鹤峰磷矿在硫、磷混酸中的溶解动力学进行了研究,考查了硫酸质量分数及反应温度对酸解过程的影响;选用考虑了自阻化因素的德罗兹多夫方程ln100/(100-Kp)-βKp%=kt描述酸解过程的动力学。研究结果表明:鹤峰磷矿在硫、磷混酸中的反应速率常数随温度升高而增加,随硫酸质量分数的增加而减小。该反应属于扩散控制,平均反应活化能约为32.7 kJ/mol。

超声波对磷矿酸解过程的强化

本文主要研究了超声波对硫酸分解磷矿过程的影响。讨论了超声的声强、时间、温度对磷矿酸解的影响。实验结果表明,磷矿分解率随着超声功率、反应时间和水浴温度的增加而提高。超声波对分解率的影响很大,特别是在酸解过程后期,可以提高16%左右。反应速率常数与温度的关系符合阿累尼乌斯方程。利用固体粒度不变的缩芯模型回归实验数据,得到宏观动力学模型。

Imaging Isocyanic Acid Photodissociation at 193 nm:the NH(a^1△)+CO(X^1∑^+)Channel

The photodissociation dynamics of isocyanic acid （HNCO） has been studied by the time- sliced velocity map ion imaging technique at 193 nm. The NH（a1△） products were measured via （2＋1） resonance enhanced multiphoton ionization. Images have been accumulated for the NH（a1△） rotational states in the ground and vibrational excited state （v=0 and 1）. The center-of-mass translational energy distribution derived from the NH（a1△） images implies that the CO vibrational distributions are inverted for most of the measured 1NH（v｜j） internal states. The anisotropic product angular distribution observed indicates a rapid dissociation process for the N-C bond cleavage. A bimodal rotational state distribution of CO（v） has been observed, this result implies that isocyanic acid dissociates in the S1 state in two different pathways.

Kinetics of Thermal Decomposition of Lithium Hexafluorophosphate

With on-line coupled thermo-gravimetric technique, the thermal decomposition of analyzer-Fourier transform infrared spectrometer lithium hexafluorophosphate （LiPF6） and its gas evolution at inert environment （H2O〈10 ppm） were studied under both non-isothermal and isothermal conditions. The results showed that the LiPF6 decomposition is a single-stage reaction with LiF as final residue and PF5 as gas product. In addition, its decomposi- tion kinetics was determined as 2D phase boundary movement （cylindrical symmetry） under both non-isothermal and isothermal conditions. Furthermore, the activation energy of LiPF6 decomposition was calculated as 104 and 92 kJ/mol for non-isothermal and isothermal con- ditions, respectively.

Isolation, Identification and Biodegradation Characteristics of a Phthalate Ester Degrading Bacterium

By using plate screening techniques with five phthalate esters （DMP, DEP, DBP, DEHP and DOP） as energy and carbon sources, an active strain was isolated from the sediments of Chaohu Lake, which was identified as Burkholderia pickettil and named B. pickettii.z-1. The biodegradation of five phthalate esters by B. pick- ettii.z-1 strain was in accordance with the pseudo first-order kinetic equation： Ct = C0.e-kt. As the concentration of phthalate esters increased, the degradation rate of phthalate esters was reduced. B. pickettii.z-1 strain exhibited remarkably different degradation effects on various PAEs. Specifically, short-side-chain DMP and DEP were degraded rapidly, while long-side-chain DBP and DEHP were degraded slowly.

Thermal Decomposition and Kinetics of Mixtures of Polylactic Acid and Biomass during Copyrolysis

Thermal decomposition of polylactic acid （PLA） was studied in the presence of pine wood sawdust （PS）, walnut shell （WS）, corncob （CC） in order to understand the pyrolytic behavior of these components occurring in waste. A thermogravimetric analyzer （TGA） was applied for monitoring the mass loss profiles under heating rate of 10℃·min^-1. Results obtained from this comprehensive investigation indicated that PLA was decomposed in the temperature range 300 -372℃, whereas the thermal degradation temperature of biomass is 183-462℃. The difference of mass loss （AW） between experimental and theoretical ones, calculated as algebraic sums of those from each separated component, is about 17%-46% at 300-400℃. These experimental results indicated a significant synergistic effect during PLA and biomass copyrolysis. Moreover, a kinetic analysis was performed to fit thermogravimetric data, the global processes being considered as one to two consecutive reactions. A reasonable fit to the experimental data was obtained for all materials and their blends.

The Study of Dissolution Kinetics of K_2SO_4 Crystal in Aqueous Ethanol Solutions with a Statistical Rate Theory

Dissolution kinetics of K2SO4 crystal in aqueous ethanol solutions was studied on-line with ion selective electrode. The concentration of K2SO4 was calculated from the determined electromotive force in which the activity coefficient of components in the liquid phase was calculated with the Pitzer equation. Dissolution kinetic parameters in the modified statistical rate theory were regressed. The correlation results show that dissolution rate of K2SO4 is slower in aqueous ethanol solutions than that in aqueous solutions. The two most important reasons are as follows: (1) The solubility of K2SO4 in aqueous ethanol solutions is lower than that in aqueous solutions, which causes a decrease of the driving force of mass transfer. (2) The process of surface reaction of K2SO4 became slower due to the addition of ethanol, so that the whole process is mainly dominated by the surface reaction instead of mass transfer.

Kinetics of Levulinic Acid Formation from Glucose Decomposition at High Temperature

Levulinic acid is a kind of new green platform chemical with wide application. The kinetics of levulinic acid formation from glucose decomposition at high temperature was investigated. Glucose containing 1%, 3% or 5% H2SO4 was treated at 170℃ or 190℃. For the various experimental conditions assayed, the time-courses of glucose and glucose degradation products (including 5-hydroxymethylfurfural and levulinic acid) were established. These variables were cor-related with the reaction time based on the equations derived from a pseudo-homogeneous, first-order kinetic model, which provided a satisfactory interpretation of the experimental results. The set of kinetic parameters from regression of experimental data provided useful information for understanding the levulinic acid formation mechanism.

Kinetics of Glucose Ethanolysis Catalyzed by Extremely Low Sulfuric Acid in Ethanol Medium

The kinetics for production of ethyl levulinate from glucose in ethanol medium was investigated. The experiments were performed in various temperatures （433-473 K） and initial glucose concentrations （0.056-0.168 mol·L-1） with extremely low sulfuric acid as the catalyst. The results show that higher temperature can improve the conversion of glucose to ethyl levulinate, with higher yield of ethyl levulinate （44.79%, by mole） obtained at 473 K for 210 min. The kinetics follows a simplified first-order kinetic model. For the main and side reactions, the values of activation energy are 122.64 and 70.97 kJ·mo1-1, and the reaction orders are 0.985 and 0.998, respectively.

Kinetics of non-catalyzed hydrolysis of tannin in high temperature liquid water

High temperature liquid water(HTLW) has drawn increasing attention as an environmentally benign medium for organic chemical reactions,especially acid-/base-catalyzed reactions. Non-catalyzed hydrolyses of gallotannin and tara tannin in HTLW for the simultaneous preparation of gallic acid(GA) and pyrogallol(PY) are under investigation in our laboratory. In this study,the hydrolysis kinetics of gallotannin and tara tannin were determined. The reaction is indicated to be a typical consecutive first-order one in which GA has formed as a main intermediate and PY as the final product. Selective decomposition of tannin in HTLW was proved to be possible by adjusting reaction temperature and time. The present results provide an important basic data and reference for the green preparation of GA and PY.

Kinetic Studies on Wheat Straw Hydrolysis to Levulinic Acid

Levulinic acid is considered as a promising green platform chemical derived from biomass.The kinetics of levulinic acid accumulation in the hydrolysis process of wheat straw was investigated in the study.Using dilute sulfuric acid as a catalyst,the kinetic experiments were performed in a temperature range of 190-230°C and an acid concentration range of 1%-5% (by mass) .A simple model of first-order series reactions was developed,which provided a satisfactory interpretation of the experimental results.The kinetics of main intermediates including sugar and 5-hydroxymethylfurfural(5-HMF) were also established.The kinetic parameters provided useful information for understanding the hydrolysis process.

Modeling of degradation kinetics of Salvianolic acid B at different temperatures and pH values

In this work,the effects of degradation time,temperature,and pH value on the degradation of Salvianolic acid B in aqueous solution were determined.Higher pH values,higher extraction temperature,and longer extraction time led to more degradation of Salvianolic acid B.Danshensu concentration increased as Salvianolic acid B degraded.A mechanism model was developed considering the degradation of Salvianolic acid E and lithospermic acid,which were two degradation products of Salvianolic acid B.The reverse reactions of Salvianolic acid B degradation were also considered.Degradation kinetic constants were calibrated.The degradation kinetics of Salvianolic acid B,lithospermic acid,and Danshensu in a Salvia miltiorrhiza extract aqueous solution were predicted using the mechanism model.The predicted concentrations agreed well with the experimental results.This model was developed using degradation data obtained from simple composition systems,but it can be applied in a complex botanical mixture with high prediction accuracy.

Thermal Decomposition Kinetics of Abietic Acid in Static Air

The thermal decomposition of abietic acid in air was investigated under non-isothermal condition using thermogravimetric analysis-differential thermal analysis （TGA-DTA） technique with heating rates of 5, 10, 15 and 25 K.min-~. The non-isothermal kinetic parameters were obtained via the analysis of the thermogravimetric and differential thermogravimetric （TG-DTG） curves by using Flynn-Wall-Ozawa method and Kissinger method. The thermal decomposition mechanism of abietic acid was studied with four integral methods （Satava-Sestak, MacCallum-Tanner, ordinary integral and Agrawal）. The results show that the thermal decomposition mechanism is nu- cleation and growth, and the mechanism function is Avrami-Erofeev equation with n equates 1/2. The activation energy and the pre-exponential factor are 64.04 kJ.mol^-1 and 5.89×10^5 s^-1, respectively.

Decomposition kinetics of zircon sand in NaOH sub-molten salt solution

Sub-molten salt was applied to the decomposition of zircon sand(ZrSiO4).The kinetics of the decomposition of zircon sand and the effects of reaction temperature,reaction time,NaOH content,agitation speed,and the NaOH/ore mass ratio on the decomposition rate of zircon sand in NaOH sub-molten salt were investigated.The results indicate that the decomposition rate of zircon sand increases with the increase in the reaction temperature,reaction time,and NaOH content.The shrinking-core model with surface chemical reaction-controlled process is the most applicable for the decomposition of zircon sand,with the apparent activation energy of 77.98 kJ/mol.The decomposition product is sodium zirconium silicate(Na2ZrSiO5),and the decomposition rate is higher than 99%under the optimal conditions.

Surface Acidity of Aluminum Phosphate and Its Catalytic Performance in Benzene Alkylation with Long Chain Olefin

The acidic properties of aluminum phosphate （A1PO4-5） solid acid catalyst were characterized by tem- perature programmed desorption （TPD） of ammonia （NH3）, n-propylamine （n-C3HTNH2）, iso-propylamine [（CH3）2CHNH2] and n-dipropylamine [（C3H7）2NH] separately, and its catalytic performance in benzene alkylation with long chain olefin was studied in a fixed-bed reactor. The characterized acid amount of catalyst increased with the basicity of adsorbates. With increase of the activation temperature of catalyst, the acid amount characterized by NHa-TPD decreased, however, it increased when characterized by TPD using three other adsorbates. The desorption kinetics of TPD process and the deactivation kinetics of catalyst were investigated. The acidity and catalytic per- formance of catalyst was also correlated. The results showed that the acid amount and strength are well correlated with the activity and stability using NH3 as adsorbate, respectively, which indicated NH3 was a better basic adsorbate. It was also found that the catalyst with higher acid amount and lower acid strength on the surface exhibited the better catalytic performance and stability.

Influence of anions in phosphate and tetraborate electrolytes on growth kinetics of microarc oxidation coatings on Ti6Al4V alloy

The growth kinetics of microarc oxidation(MAO)coatings on Ti6Al4V alloy was studied by designing an electrolyte with low PO_(4)^(3−)content and high B_(4)O_(7)^(2−)content,using scanning electron microscopy,transmission electron microscopy,X-ray diffraction,and potentiodynamic polarization.The results showed that B_(4)O_(7)^(2−)increased the spark intensity and dissolved most of the oxides at high temperatures.Then,a thicker barrier layer at the coating/substrate interface was produced,which increased the polarization resistance of the coating.PO_(4)^(3−)at a low concentration also promoted the uniform growth of the MAO coating and the formation of hat-shaped holes in the outer deposition layer.The thickness of the MAO coatings obtained in Na_(2)B_(4)O_(7) electrolytes exhibited an exponential increase with time at spark discharge stage,while that of the MAO coating obtained in phosphate–tetraborate electrolytes showed a linear trend as the PO_(4)^(3−)content increased.