磷酸脲离解反应的热力学研究

磷酸脲可作为反刍动物饲料添加剂和青贮饲料保藏剂,高浓度NP复合肥、聚磷酸和净化湿法磷酸的中间体,以及阻燃剂、清洗剂等。国外众多研究者对磷酸脲结构、性能和应用进行了广泛的研究。但对磷酸脲离解反应的热力学研究甚少,尚未见详尽报道。本文就磷酸脲     

萃余酸萃取法制高纯磷酸二氢钾研究

采用湿法磷酸净化工艺产生的副产物萃余酸为磷源,以低廉的氯化钾为钾源,研究如何通过一系列萃取与复分解反应制备高纯磷酸二氢钾的技术。重点研究搅拌速度、反应时间、反应温度、KCl用量、KCl初始质量浓度等单因素对P2O5转化率的影响,并通过正交组合实验进一步确立了最佳反应条件。按照该工艺条件采用湿法萃余磷酸制备高纯磷酸二氢钾兼具了反应条件温和、能耗非常低以及可显著降低成本等诸多优点,故值得在磷酸盐工业中推广其应用。     

磷酸钾中和法邻甲酚羧化反应的绿色合成

以邻甲酚和二氧化碳为原料,以磷酸钾为中和剂一步羧化合成邻甲基水杨酸及相关产物。探讨了反应条件对产率的影响。实验结果表明,当磷酸钾与邻甲酚物料比为2.5∶1,反应温度150 ℃,反应压力3.0 MPa时,羧化反应产物总收率达到95.4%,同时邻甲基水杨酸收率也达到最大。与传统碳酸钾中和法相比,磷酸钾中和法产物在后处理过程中无二氧化碳放出,后处理过程中的磷酸根可制备为磷酸钾使用,新工艺是一条绿色化工路线。     

以次磷酸镍为原料制备NiP和NiPB非晶态合金的新方法

以次磷酸镍为原料用化学还原法制备出了NiP和NiPB非晶态合金.用ICP、XRD和TEM等方法对催化剂物性进行了表征.研究了制备条件，如原料浓度、温度、pH值及引发剂的加入对制备NiP非晶态合金的影响.在300 K下所制备的NiP非晶态合金平均粒径约为30 nm.研究了原料浓度与原料配比对NiPB非晶态合金物性的影响，可通过改变原料浓度和配比得到所需组成的NiPB非晶态合金. NiPB非晶合金平均粒径约为15 nm.     

2-取代苯并眯唑合成工艺的改进

以邻苯二胺和有机酸为原料,在磷酸和多聚磷酸混合酸的催化下合成了四种2-取代苯并咪唑化合物。利用红外光谱、核磁氢谱、熔点测定等方法对产物进行了结构表征。讨论了反应温度、催化剂用量对收率的影响。该合成工艺较原有的工艺得以完善,收率有较大提高。     

溶胶-凝胶法制备纳米二氧化钛颗粒的研究

本文采用钛酸丁脂等原料,利用sol-gel方法制备了TiO2纳米颗粒.研究了不同实验顺序(滴入方式)和工艺参数对制备效果的影响.通过实验和对TiO2纳米粉末的TEM分析,获得了粒度(30-40nm)比较均匀的球型TiO2纳米颗粒.     

湿法磷酸生产过程中控制稀土走向的研究

采用稀土含量0．55％REO磷矿为原料在间歇实验装置中进行二水物湿法磷酸模拟生产,研究了湿法磷酸生产中工艺条件及活性添加剂对磷矿中稀土走向的影响。研究结果表明：较低的体系温度、高的磷酸浓度及较大的液固比均有利于稀土在磷酸中的富集;控制合适的SO^2-4浓度有利于硫酸钙晶体的成长,可减少磷酸稀土的共晶和吸附作用,从而提高稀土的浸出率,在硫酸与磷矿的化学计量比为1.1时可形成易于洗涤和过滤的类球状聚晶;通过添加活性添加剂控制硫酸钙的结晶速度和结晶形貌,从而减少磷酸稀土和硫酸钙的共晶和吸附作用,以提高稀土在磷酸中的富集;添加不同活性添加剂,稀土在磷酸中的富集程度不同,其中以NS-2,NS-1及IA-1对稀土在磷酸中的富集影响尤著,稀土总浸出率可达75％以上。     

药学本科实验类型及其教学方法的改革

介绍在药学本科实验类型及其教学方法改革所作的一点探索。在学生实验中以相同的原料、类似的试剂,分别采用传统加热化学合成方法与微波辐射合成方法合成同一药物中间体,引导学生就制备工艺、实验结果的差异进行对比讨论,以提高学生的学习兴趣,保证实验教学质量。     

含全氟壬烯基磷酸酯型表面活性剂的合成

以N-羟乙基-p-全氟壬烯氧基苯甲酰胺(I)为原料与三氯氧磷(POCl3)反应制备p-全氟壬烯氧基苯甲酰胺基乙基磷酰氯,反应结束后在常温下进行水解生成p-全氟壬烯氧基苯甲酰胺基乙基磷酸单酯(Ⅱ)。采用红外光谱(FTIR)、1HNMR、质谱(MS-ESI)对其结构进行了表征。考察了酯化反应时间、酯化反应温度、原料配比和缚酸剂对产物收率的影响。通过单因素实验和正交试验对反应进行优化,确定了最佳合成工艺条件为:n(I):n(POCl3)=1:1.6,反应温度70℃,反应时间7h,三乙胺做为缚酸剂,在此条件下Ⅱ的收率为84.3%。     

磷酸锆镍的微波制备及其可见光光催化性能

以氧氯化锆、氯化镍和磷酸二氢钠为原料,在较低温度和常压条件下采用微波辅助法制备具有特殊形貌的磷酸锆镍NiZr(PO_4)_2·4H_2O。研究了3种不同种类的表面活性剂对磷酸锆镍的物相、尺寸及形貌的影响。结果表明,表面活性剂的引入可以降低磷酸锆镍颗粒的平均粒径。与十二烷基硫酸钠(SDS)相比,聚乙烯吡咯烷酮K30(PVP-K30)和十六烷基三甲基溴化铵(CTAB)对颗粒生长的抑制程度更大,从而产物的平均粒径更小。使用亚甲基蓝(MB)溶液模拟印染废水,对磷酸锆镍的光催化降解性能进行了探讨。结果表明,可见光下以PVP-K30为模板制备的磷酸锆镍对MB的表观脱色率为49.0%,优于CTAB和SDS条件下制备的磷酸锆镍。本文为新型磷酸锆类复盐的制备与应用研究提供了新的思路和方法。     

A calibration algorithm for atomic absorption

The equation

is shown to be applicable in fitting the analytically useful concentration range of atomic absorption calibration curves. In this equation C is the concentration, A the observed absorbance, and the K's are coefficients which must be determined during calibration. Typical calibration data for four diverse elements (Ag, Bi, Co and Cu) determined in an air-acetylene flame are shown and rules for choosing the standards to be used are discussed.     

An experimental and theoretical study of the PVT equation of state of butadiene and isoprene elastomers to 200°C and 200 MPa

We have performed and analyzed extensive pressure-volume-temperature (PVT) measurements on uncrosslinked polybutadiene and polyisoprene elastomers from ambient temperature to about 200°C and 200 MPa. In the polybutadiene series, 1,2 content varied from 8 to 87%, the remainder being similar amounts of cis-1,4 and trans-1,4. In the polyisoprene series the 3,4 content varied from 8 to 64%, the trans-1,4 content was 12–16%, and the remainder was cis-1,4, with < 4% 1,2 content. We report parameters describing the experimental data in terms of the empirical Tait equation, the cell model, the Simha-Som-cynsky equation, the Sanchez-Lacombe, and the Flory-Orwoll-Vrij models. In general the parameters show systematic changes with the microstructure content. The agreement between theory and experiment is excellent for the Tait equation, and also for the Simha-Somcynsky model and the cell model. The maximum deviation between theory and experiment was less than 0.004 cm³/g for the Simha-Somcynsky theory, and less than 0.005 cm³/g for the cell model. Average absolute deviations are three to four times less. For the Sanchez-Lacombe and the Flory-Orwoll-Vrij models, the maximum deviations are 5–8 times as large, and very systematic. Parameter derived from the Simha-Somcynsky theory are discussed with respect to the microstructure, and with respect to the glass transition of these two series of materials. © 1993 John Wiley & Sons, Inc.     

Modified Karplus equations and their stereochemical applications

The current status of research on the Karplus equation for the vicinal spin—spin coupling constants (SSCC)³ J _HH, of fundamental significance in applications of NMR spectroscopy for establishing the configuration and conformational features of organic compounds in solutions, is discussed in the review. The data on the analysis of the fundamental molecular factors that affect the³ J _HH SSCC were generalized: the dihedral angle between interacting protons, the electronegativities of - and -substituents, the H-C-C valence angles, the C-C bond length, and effects of "proximity of substituents." The stereochemical applications of different modifications of the Karplus equation proposed in recent years were examined and comparatively analyzed. Possible ways of improving the accuracy of predicting the³ J _HH SSCC by using modern modifications of the Karplus equation and the method of molecular mechanics were discussed.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1483–1506, July, 1992.     

(p, Vm, T) measurements of (cyclohexane + nonane) at temperatures from 298.15 K to 328.15 K and at pressures up to 40 MPa

The densities and speeds of sound of (cyclohexane + nonane) were measured at four temperatures from 298.15 K to 328.15 K, and the respective values of excess volumes and adiabatic compressibility were calculated. Thereafter, the densities for the last system were measured at elevated pressures (0.1 to 40) MPa at four temperatures over the range 298.15 K to 328.15 K with a high-pressure apparatus. The high-pressure density data were fitted to the Tait equation and the isothermal compressibilities were calculated with a novel procedure with the aid of this equation. The low- and high-pressure values of calculated from the density data show that the deviations from ideal behaviour in the system decrease slightly as the temperature and pressure are raised. The data were fitted to the fourth-order Redlich-Kister equation, with the maximum likelihood principle being applied for the determination of the adjustable parameters.     

ADSORPTION OF GOLD ON TBP EXTRACTING RESIN FROM HCI SOLUTION

Solventextractionandadsorption,asordinarymethodsofretrievinggoldfromwasteliquid,havetheshortcomingsofthedifficultyofsolventrecoveryandlimitingadsorptioncapacityrespectively.Fixingtheextractionsolventinthesmallopeningsoftheadsorptionresintoformtheextractingresin,thentoadsorbsoluteinsolution,partakesofcharacteristicsofbothsolventextractionandad.sorption,remedyingthedefectsoftheabovementionedtwo..th.d.[IJ.Extractingresincontaining50%tributylphosphate(TBP)hasbeenusedinextractionchromatographyfor…     

The mixing properties of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl) cyclotrisiloxane with various organosilicon compounds at different temperatures

The density and refractive index were determined for four binary mixtures of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl) cyclotrisiloxane with octamethyl-cyclotetrasiloxane, hexamethyldisiloxane, 2,4,6,8-tetramethyl-cyclotetrasiloxane and 2,4,6,8-tetramethyl-2,4,6,8-tetraethenylcyclotetrasiloxane at different temperatures T = (308.15, 313.15, 318.15, 323.15 and 328.15) K and atmospheric pressure using a DMA4500/RXA170 combined system. The excess molar volume, partial excess volume at infinite dilution, isobaric coefficient of thermal expansion, excess refraction indices, Lorentz–Lorenz molar refraction and the deviation in molar refraction have been calculated using this data. The results have been incorporated into the Redlich–Kister equation and used to estimate the binary interaction parameters and standard deviation. The values of partial excess volume at infinite dilution and excess refraction indices for the four binary systems at different temperatures were calculated using the adjustable parameters of the Redlich–Kister smoothing equation. The factors that affect these excess quantities are discussed.     

ADSORPTION OF GOLD ON TBP EXTRACTING RESIN FROM HCl SOLUTION

Adsorption of gold on TBP extracting resin from HCl solution was researched.All the effects of factors,such as solution acidity,TBP content,temperature,etc.,on adsorption equilibrium were discussed and the equilibrium equation was formulated.The breakthough time of adsorption process with fixed bed was studied through experiment.     

Theoretical analysis of oriented and non-isothermal crystallization III. Kinetics of crystal orientation

Summary A general orientation equation for rigid particles embedded in a continuum has been derived. The equation includes hydrodynamic, thermodynamic, diffusional and kinetic terms, corresponding to physically different orientation mechanisms. Some special solutions of the general equation are presented, and discussed conditions under which the general equation reduces to more simple cases. Numerical examples of orientation in polyethylene subjected to uniaxial forces are discussed.With 6 figuresSome results contained in this paper have been presented before the V-th Europhysics Conference on Macromolecular Physics Orientation Effects in Solid Polymers, Budapest, April 1976.     

The study of esterifying reaction between epoxy resins and carboxyl acrylic polymers in the presence of tertiary amine

In this article, the fixed gel/nongel point and critical gel point experiments are designed for formulating the regulation of esterification reaction between epoxy resin and carboxyl acrylic polymer in the presence of tertiary amine in organic solvent. Ternary diagrams are employed to illustrate experimental results. It is disclosed that some factors, such as mole ratio of the ternary reactants, molecular weight of epoxy resin, even the hydrophilic solvent content of system, play important roles in the gelling effect of esterification reaction. In order to explain these experimental results, a suggested reaction process is put forward and, subsequently, a critical gel equation is derived from Carothers gelation theory. The equation provides an explicit connection between the critical gel composition and the relevant parameters of the reaction system such as average carboxyl functionality of acrylic resin, average molecular weight of epoxy resin, the base intensity of tertiary amine, and the solid content of system. The regressive critical gel curve based on the equation is well consistent with the experiment data. It expresses that the suggested reaction process is reasonable. Finally, based on the critical gel equation, the important factors that influence the esterification result are discussed qualitatively. All the achievements are beneficial to understanding the reaction process and avoiding useless gelation in preparing the water-reducible compositions.     

Chemometrically assisted optimization and validation of a new HPLC method for the determination of paliperidone in pharmaceuticals

Paliperidone is an antipsychotic drug, which is used for the acute and maintenance treatment of schizophrenia. In this study, a new method was developed for the determination of Paliperidone in its extended-release tablets. Face-centered central composite design was applied for optimization of the method. Factors were decided as acetonitrile content, pH of the mobile phase and buffer concentration through preliminary studies. Optimal flow rate (1?mL/min), column temperature (35°C) and internal standard (Bupropion) were also determined during preliminary studies. Retention factors and tailing factors of Paliperidone and Bupropion were selected as responses. Derringer’s desirability function was applied for simultaneously optimization of these four responses. Optimal conditions were predicted as phosphate buffer (pH:3, 23?mM): acetonitrile (76:24, v:v). Developed method was validated in terms of linearity, detection and quantification limits, accuracy, precision, specificity and robustness. Method was found linear in the concentration range of 0.125-100?µg/mL. Mean equation of the calibration curve was y?=?0.0807 x - 0.0102 (R²?=?0.9999). Accuracy and precision of the method was evaluated with recovery values (98-102%) and relative standard deviation values (<2%), respectively. All other parameters were found acceptable. The method was successfully applied for the determination of Paliperidone in its extended-release tablets.