癸酸-十四烷酸二元体系的相变性能

以癸酸(CA)-十四烷酸(MA)二元体系的理论预测相图为指导, 测量了该体系不同组成超声波混合后的步冷曲线, 绘制了该体系的实验相图, 判断出最低共熔温度与组成范围; 采用DSC测试最低共熔组成的相变性能, 采用IR检测最低共熔组成300次热循环前后的波形变化. 实验结果表明, CA-MA二元体系最低共熔组成范围为(76%~82%)CA+(24%~18%)MA, 最低共熔温度为294.45 K, 最大过冷度为274.75 K, 相变过程中无分层现象; DSC和IR的测试结果表明, 组成为78%CA+22%MA的相变焓为149.02 J/g, 开始相变温度为292.80 K, 热稳定性好.     

Binary melting phase diagrams of nifedipine-PEG 4000 and nifedipine-mannitol systems

The phase diagrams of nifedipine-polyethylene glycol (PEG) 4000 and nifedipine-mannitol systems have been determined. Heating experiments on thermodynamically equilibrated co-melts revealed eutectic behaviour for nifedipine-PEG 4000 mixtures, with the composition of the eutectic point between 40 and 45%w/w of nifedipine. These observations were supported by optical and hot stage microscopy. Nifedipine and mannitol were negligibly miscible in the solid-state, behaving as a binary system with monotectic characteristics. Application of phase diagrams to the production of solid dispersions is shown to be rational, since they provide valuable information on the state of the binary systems under preparation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase Diagram of EC–DMC Binary System and Enthalpic Determination of Its Eutectic Composition

We construct with a differential scanning calorimeter (DSC) a phase diagram for the ethylene carbonate (EC)-dimethyl carbonate (DMC) binary system for its liquid-solid phase equilibria. We determine the eutectic composition of the binary system using an enthalpic method that we devised based on the composition dependence of the enthalpy of solidus melting, with highly consistent results. We also discuss the merits and limitations of this enthalpic method. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal investigation of PEG 4000 — oxazepam binary system

A thermal study using DSC and Hot Stage Microscopy (HSM) was carried out to investigate the interaction in solid state of the binary system PEG 4000 — oxazepam, and to establish their phase diagram. The eutectic composition, which melting occurs at lower temperature as compared with the pure components, has been determined. The results obtained by DSC and HSM have indicated that PEG 4000 — oxazepam mixtures displays no obvious incompatibilities, and that the system shows a typical eutectic behaviour. However because of the closeness of the melting of PEG 4000 to the eutectic temperature, it was difficult to determine precisely the eutectic composition and temperature on the basis of DSC measurements alone. The use of heats of fusion corresponding to physical mixtures allowed an estimation of the eutectic composition at 6% w/w oxazepam. Additional information of temperature (57.6C) and composition (5–10% w/w oxazepam) of the eutectic was obtained by HSM using the contact method. This low melting temperature in this range of compositions offers advantages in terms of drug stability and easy manufacture.     

Congruent melting of binary compounds with non-negligible vapour pressure

The sulfaguanidine—water (SG-H₂O) system is a binary system with non-negligible vapour pressure which presents a monohydrate. The phase diagram of this system is drawn from DTA experimental results, using the temperature-specific volume-molar fraction (T-v-x) model which was described in part I of this work. The melting of the monohydrate (SG, H₂O) is found to be congruent. Isochoric sections are drawn; they make it possible to determine the limits of the two eutectic invariant planes. The composition and specific volume of the vapour phase at the eutectic equilibrium of theSG-SG, H₂O subsystem are given. The triple line solid-liquid-vapour of the one-component phase diagram of the monohydrate is drawn. The experimental results are consistent with the congruent melting of the monohydrate. These results also show that the solid, liquid and vapour phase at the triple line have not the same composition.     

癸二醇和十二烷二醇及其混合物的液固相变研究

使用差示扫描量热法（DSC）和红外光谱法（IR）对1，10-癸二醇（1，10-C10H22O2，A）与1，12-十二烷二醇（1，12-C12H26O2，B）及其二元混合物系统液固相变进行研究。测定了该二元混合系统的相变温度、相变焓和液固平衡相图。该二元系统存在低共熔混合物，其组成为xB=0．333，低共熔温度为328K。该二元混合系统的IR图谱显示存在氢键缔合现象，长链烷烃中的亚甲基在晶格中是有序规则排列的。该系统具有较低的相变温度和较高的相变焓，是一种潜在的低温储能材料。     

Thermal analysis of the system triamterene-d-mannitol

Thermal analysis (DSC and HSM), and equilibrium solubility determinations were carried out to elucidate the mechanism of interaction at the solid state in the binary system triamterene-D-mannitol. Physical mixtures (5–90% w/w triamterene) and solid dispersions (5 up to 40% w/w triamterene) were prepared and studied. From DSC and HSM results, the thermal changes were associated with the variations in composition of the binary mixture, being more pronounced in the range 20–50% w/w. The binary phase diagram was proposed, although the exact position of the eutectic was uncertain. This is in accordance with a partial dissolution process detected by HSM. A linear increase in the solubility of triamterene with increasing aqueous mannitol concentration was obtained. The thermodynamic parameters of the solution properties were calculated, with an activation energy value of 96.081 kJ/mole. The solubilization increase was associated with complexation processes and hydrogen bonding formation. Dedicated to Professor Lisa Heller-Kallai on the occasion of her 65^th birthday     

Phase diagram study of CaBr2–CaHBr system

A study of binary, CaBr₂–CaHBr system was carried out by differential thermal analysis (DTA), covering the composition range from 100 % CaBr₂ to 100 % CaHBr between room temperature and 800 °C. From DTA results, the contour of solidus and liquidus temperatures with composition is plotted and the phase diagram of CaBr₂–CaHBr system is constructed. The system shows an eutectic reaction at 576 °C and the eutectic composition is 79.6 mol% CaBr₂. Co-existing phases in different phase fields are characterized by X-ray diffraction analysis.     

The phase diagram of CsNO<Subscript>3</Subscript>–RbNO<Subscript>3</Subscript>

The phase transitions of RbNO₃ and the binary phase diagram of (Cs,Rb)NO₃ were investigated at atmospheric pressure, using simultaneous direct and differential thermal analysis, μDTA and DSC techniques. A fourth phase transition of RbNO₃ has been observed at temperature near the melting point. The phase diagram of this system is characterised by a eutectic, two eutectoid and an azeotropic-like invariants. Three limited solid solutions and two continuous solid solutions have been detected at low temperature.     

YbCl3-MCln体系相图的研究(M=Li、Mg、Ca、Pb; n=1,2)

借助于DTA与X射线衍射法研究了YbCl_3-MCl_n(M=Li、Mg、Ca、Pb; n=1或2)二元体系相图．发现YbCl_3-LiCl体系相图属固液异组成型，有化合物Li_3YbCl_6生成，它在481 ℃有一相转变. 其无变点分别为x_(YbCl_s)＝0.410；526 ℃和x_(YbCl_3)=0.340，547 ℃；YbCl_3-MgCl_2属类转熔型相图，在富YbCl_3相区666 ℃有一尚不知其性质的热效应，为x_(YbCl_3)＝0.380，628 ℃；YbCl_3-CaCl_2和YbCl_3-PbCl_2体系皆属简单低共熔型相图，其低共溶点分别为x_(YbCl_3)＝0.530, 615 ℃和x_(YbCl_3)＝0.340, 415 ℃. 后者在固相下有一不稳定化合物PbYbCl_5生成，在392 ℃分解，同时探讨了相图的某些规律．     

Diagramme De Phases Du Systeme Binaire CsNO3—LiNO3. Activité des constituants du liquide

Phase diagram of the binary system CsNO₃–LiNO₃ has been drawn by using simultaneously direct and differential thermal analysis between 323 and 723 K. This system is characterized by a congruent intermediate equimolar compound with melting point at 463 K, two eutectic reactions at 447 and 433 K; the eutectic points are respectively at 0,47 and 0,63 mol fraction of LiNO₃; a plateau due to the phase transition of CsNO₃ at 428 K and an other one at 333 K due to the formation of CsLi(NO₃)₂. The miscibility in solid state seems to be nil or negligible. These results associated with some other thermodynamic data have been used to calculate the activities of the constituents along the liquidus curve and the activities of the liquid constituents at 723 K. The binary liquid (Cs–Li)NO₃ exhibits a negative deviation from the ideal behaviour.This revised version was published online in November 2005 with corrections to the Cover Date.     

Prediction and experimental determination of the binary and ternary phase diagrams of (±)medetomidine hydrochloride

The binary phase diagram of medetomidine hydrochloride was determined based on thermogravimetric differential thermal (TGA/DTA) measurements. The binary phase diagram presented a eutectic point in the 19:81 [(R)/(S)] composition and the ternary phase diagram in the presence of 2-propanol showed a eutectic point in the 75:25 [(S)/(R)] composition, both characterizing the product as a racemic compound forming system. The solubility of enantiomeric mixtures in 2-propanol was measured at 10, 20 and 30 °C. The ideal solubility curves of the mixtures were calculated and the activity coefficients derived. A semi-empirical thermodynamic model UNIversal QUAsi-Chemical (UNIQUAC) was used to predict the solubility of various compositions of enantiomers at different temperatures. There was good agreement between the experimental solubility data of medetomidine hydrochloride and the results obtained from the UNIQUAC equation.     

Thermal and conductometric studies of NdBr3 and NdBr3-LiBr binary system

The heat capacity of solid NdBr₃ was measured by Differential Scanning Calorimetry in the temperature range from 300 K up to the melting temperature. The heat capacity of liquid NdBr₃ was also determined. These results were least-squares fitted to a temperature polynome. The melting enthalpy of NdBr₃ was measured separately. DSC was used also to study phase equilibrium in the NdBr₃-LiBr system. The results obtained provided a basis for constructing the phase diagram of the system under investigation. It represents a typical example of simple eutectic system. The eutectic composition, x(NdBr₃)=0.278, was obtained from the Tamman construction. This eutectic mixture melts at 678 K. The electrical conductivity of NdBr₃-LiBr liquid mixtures and of pure components was measured down to temperatures below solidification. Reflectance spectra of the pure components and their solid mixtures (after homogenisation in the liquid state) with different composition were recorded in order to confirm the reliability of the constructed phase diagram. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal analysis of the system KCL-LiCI by differential scanning calorimetry

Thermal analysis of the binary system KCl-LiCl in the composition range 0.368–0.812 mol fraction of LiCl was studied by differential scanning calorimetry (DSC). On the basis of the DSC curves, the experimental data for the phase-diagram, the latent heat of fusion, and the average specific heat in the liquid and solid states are presented as a function of the composition of the mixture. The experimental results compared with literature data. The following empirical correlation between the heat of fusion (H) and of compositions of the mixture in mol fraction of LiCl (x) was obtained: ·GH=26.95–50.20x+43.06x² with a minimum value of 11.8 kJ(g mol)^–1 at the eutectic point of 0.587 mol fraction of LiCl at 354.4°C. These results are required as basic data to develop thermal energy storage materials, based on the phase change of a molten mixture of KCl-LiCI.     

Phase diagrams and water activities of aqueous dicarboxylic acid systems of atmospheric importance

We have studied liquid/solid phase diagrams and water activities of the dicarboxylic acid/water binary systems for maleic, dl-malic, glutaric, and succinc acids using differential scanning calorimetry, infrared (IR) spectroscopy of thin films, and conductivity analysis of saturated solutions. For each binary system we report the measurements of the ice melting envelope, the acid dissolution envelope, and the ice/acid eutectic temperature and composition. Water activities have been determined by using the freezing point depression of ice. Additionally, an irreversible solid/solid phase transition for maleic acid was observed in both DSC and IR studies likely due to the conversion of a meta-stable crystal form of maleic acid to its most stable crystal form. In general we find good agreement with literature values for temperature-dependent acid solubilities.     

Solid–liquid equilibrium, thermal, and physicochemical studies on salicylamide–4-nitrophenol and 2-cyanoacetamide–4-aminoacetophenone organic eutectic systems

The solid–liquid phase equilibrium data of two binary organic systems, namely, salicylamide–4-nitrophenol and 2-cyanoacetamide–4-aminoacetophenone show the formation of a eutectic in each case. The values of enthalpy of fusion of pure components and binary eutectics have been determined using differential scanning calorimeter (Mettler DSC-4000 system). The thermal properties of the materials, such as, heat of mixing, entropy of fusion, roughness parameter, interfacial energy, and excess thermodynamic functions were computed using the enthalpy of fusion values. The microstructures of eutectics were developed using unidirectional thermal gradient, and regions of interest for microstructures were photographed.     

Phase equilibria in the ternary system NaF–KF–CsF

The ternary eutectic system CsF–KF–NaF was studied by differential thermal analysis. The melting point and composition of the ternary eutectic were determined, and so was the boundary of the region of limited series of solid solutions within the composition triangle. The compositions of crystallizing phases were confirmed by X-ray powder diffraction analysis. The specific enthalpy of melting of the ternary eutectic was experimentally found.     

芴和芴酮最低共熔点的测定

采用X-4数字显示显微熔点测定仪测定了不同组成的芴与芴酮混合物试样的熔点,用最小二乘法近似处理组成与熔点数据,得到芴和芴酮的最低共熔点为57.4°C,其摩尔分数为芴39%和芴酮61%。该测定芴与芴酮最低共熔点的简单方法,可用于本科生的基础化学实验教学。     

Merit of estimations from DSC measurements for the efficiency of optical resolutions

Chiral drugs are generally resolved through formation of diastereoisomeric salts of different solubility. When the diastereoisomer salts from a eutectic in the solid phase, a good estimate can be made for the efficiency of the resolution (S), through a calculation based on the eutectic composition (x _eu). The eutectic composition can be computed from thermal data of a differential scanning calorimetric (DSC) measurement of the diastereoisomeric salts [1]. In this work we investigated the influence of uncertainties of thermal data on the estimation of the efficiency of resolution (S), spreading throughout the calculations involved. Performance of our error-estimating method is demonstrated on 6 diastereoisomer salt pairs. The obtained deviations are close to the deviations of resolution experiments. Thus, it can be concluded that the DSC measurements are useful means in predicting the efficiency of resolutions. Deceased     

Thermal,spectroscopic, and dissolution studies of ketoconazole–Pluronic F127 system

One strategy for improving the dissolution of poorly water soluble drugs is to prepare solid dispersions such as binary mixtures with hydrophilic carriers. These mixtures are generally characterized by better solubility than those of the individual components from which they are formed. In the present study, solid dispersions of ketoconazole (KET) with Pluronic F127 (PLU) were prepared by the grinding method. Solid–liquid equilibria in the system being studied were investigated by differential scanning calorimetry. A phase diagram for the whole range of compositions was constructed. The investigation revealed that ketoconazole and Pluronic F127 form a simple eutectic system containing 4.4 % w/w of ketoconazole at the eutectic point. The results of Fourier transform infrared spectroscopy and X-ray powder diffractometry studies of obtained mixtures suggest that there is no drug-carrier interaction and both components are crystalline in the solid dispersion with the whole range of composition. The prepared mixtures show an appreciable improvement of the dissolution rate of KET in 0.5 % w/v sodium lauryl sulfate. The improvement of the dissolution rate of drug is additionally increased by effective solubilization.