水+甲烷系统的气液相边界曲线和临界线(英文)

采用带有蓝宝石视窗和磁力搅拌的可变体积高压斧得出了水+甲烷系统的气液相边界曲线和临界曲线.实验温度为433.0-633.0K,实验压力为30.00-300.00MPa.实验确定了甲烷在富水区的亨利系数,结果显示,在433.0-603.0K的温度范围内,此亨利系数随着温度的升高而下降.本文还研究了甲烷+水系统的气液分配比以及偏摩尔溶解焓和偏摩尔溶解熵数据.结果发现,甲烷和水的内聚能密度差别很大.     

氢气在乙酰丙酸+水+γ-戊内酯中的溶解度

在温度353.2～453.2K、压力0.75～5.25MPa的条件下,采用平衡取样的方法,测定了氢气在不同组成(xi为摩尔分数)的四种液体乙酰丙酸、乙酰丙酸(x1=0.37)+水(x2=0.63)、γ-戊内酯、乙酰丙酸(x1=0.33)+水(x2=0.33)+γ-戊内酯(x3=0.34)中的溶解度.根据亨利定律对实验数据进行关联,得出不同温度下氢气在液体中的亨利系数,通过亨利系数和温度的关系,计算出氢气在液体中的摩尔溶解焓和摩尔溶解熵.结果表明:在实验温度、压力范围内,提高温度、增加压力,氢气在四种不同液体中的溶解度皆增大;在温度和压力相同时,氢气在四种液体乙酰丙酸(x1=0.37)+水(x2=0.63)、乙酰丙酸、乙酰丙酸(x1=0.33)+水(x2=0.33)+γ-戊内酯(x3=0.34)和γ-戊内酯中的溶解度依次增大;氢气在四种液体中的亨利系数均随着温度的升高而减小;氢气在四种液体中的摩尔溶解焓为正值,摩尔溶解熵为负值.     

甲烷在水-叔丁醇混合溶剂中的溶解度

在303.15 K、313.15 K、323.15 K、333.15 K温度下，0－6 MPa压力范围内测定了甲烷在水－叔丁醇混合溶剂中的溶解度．溶剂中叔丁醇的摩尔分数(x_(TBA))从0到1．结果表明，在温度和溶剂组成一定条件下，甲烷的溶解度随其分区的增加而增大，随x_(TBA)的增加，在富水区内，甲烷的溶解度变化较缓慢，当x_(TBA)超过某值时，甲烷的溶解度随x_(TBA)的增加而增大，并且幅度较大；在x_(TBA)约为0－0.045范围内，甲烷的溶解度随温度增加而减小，x_(TBA)约在0.045－0.15范围内，溶解度随温度增加而增加，x_(TBA)约在0.15～1.0范围内，溶解度随温度增加而减小．根据溶解度与温度和溶剂组成的关系可以推测，在303.15－333.15 K、0－6 MPa范围内，水－叙丁醇混合溶剂中仍存在笼合物结构．根据溶解度与温度、压力的关系讨论了甲烷在此混合溶剂中的亨利常数、偏摩尔体积、标准溶解自由能、标准溶解焓和标准溶解熵．     

乙二胺盐酸盐的低温热容和热化学性质

合成了乙二胺盐酸盐, 并表征了其晶体结构. 测定了其在78~370 K温度区间的低温热容, 通过最小二乘法拟合得到热容对温度的多项式方程. 设计了合理的热化学循环, 测定了所设计反应的反应物和产物的溶解焓, 得到反应焓. 利用Hess定律计算出乙二胺盐酸盐的标准摩尔生成焓为-(540.74±1.33) kJ/mol. 利用紫外-可见光谱和折光指数的结果检验了所设计热化学循环的可靠性.     

烟酸钠Na(C6H4NO2)(s)的低温热容和热化学

选择分析纯烟酸和无水醋酸钠作为反应物, 用室温固相合成方法合成了无水烟酸钠. 利用FTIR和X射线粉末衍射等方法进行了表征, 利用化学分析和元素分析确定其组成为Na(C6H4NO2). 用精密自动绝热热量计测量其在78~400 K温度区间的低温热容. 研究结果表明, 该化合物在此温度区间无热异常现象发生. 用最小二乘法将实验摩尔热容对温度进行拟合, 得到热容随温度变化的多项式方程. 用此方程进行数值积分, 得到在此温度区间每隔5 K的舒平热容值和相对于298.15 K时的热力学函数值. 在此基础上, 通过设计合理的热化学循环, 选用1 mol/L NaOH溶液作为量热溶剂, 利用等温环境溶解-反应热量计分别测得固相反应的反应物和产物在所选溶剂中的溶解焓, 得到固相反应的反应焓. 最后, 计算出无水烟酸钠的标准摩尔生成焓为: ΔfHm0[Na(C6H4NO2), s]=-(548.96±1.11) kJ/mol.     

DMA+AOT+正辛烷三组分非水微乳体系的临界现象

采用折射率法在离临界温度7 K的范围内测定N,N-二甲基乙酰胺(DMA)与二-(2-乙基己基)琥珀酸酯磺酸钠(AOT)摩尔比为3.46的非水微乳体系(DMA+AOT+正辛烷)的温度-折射率(T-n)共存曲线, 利用标准曲线转化为温度-体积分数(T-φ)共存曲线和温度-有效体积分数(T-ψ)共存曲线, 进而求得临界指数β. 研究结果表明, 该体系的临界指数β与已经报道的微乳液不同, 在较宽的温度范围内均符合Fisher重整化理论值0.365. 分析实验数据, 获得指数因子B、Wegner校正项因子B1和共存曲线的直径籽d, 并讨论所选择的序参量的优劣性.     

溶剂化的热力学集团展开理论

把二元溶液的过剩内能（excess energy）分成溶剂-溶剂、溶剂-溶质及溶质-溶质相互作用部分。利用集团展开方法给出了二元溶液在正则系综的配分函数的表达式,利用该表达式得到了溶质的偏摩尔内能(partial molar energy)和偏摩尔熵(partial molar entropy)的表达式。在无限稀溶液情形,过剩偏摩尔内能的溶剂-溶剂部分又称重组织内能（reorganization energy）,它反映了溶质存在时对其周围溶剂分子之间的相互作用能的影响。研究表明,在溶质的粒子数密度相对较大时,溶质分子之间的相互作用将影响过剩偏摩尔内能的溶剂-溶剂部分,对于稀溶液,过剩偏摩尔内能的溶剂-溶剂部分与溶质的摩尔分数成线性关系。对低密度二元溶液,溶质的过剩偏摩尔内能和过剩偏摩尔熵也与溶质的摩尔分数成线性关系。     

配合物Zn(Met)SO4·H2O(s)的低温热容和标准摩尔生成焓

利用精密自动绝热热量计直接测定了配合物Zn(Met)SO4·H2O(s)在78～370K温区的摩尔热容.通过热容曲线的解析得到该配合物的起始脱水温度为T0=329.50K.将该温区的摩尔热容实验值用最小二乘法拟合得到摩尔热容(Cp,m)对温度(T)的多项式方程,并且在此基础上计算出了它的舒平热容值和各种热力学函数值.依据Hess定律,通过设计热化学循环,选择体积为100cm3、浓度为2mol·L-1的盐酸作为量热溶剂,利用等温环境溶解-反应热量计,测定和推算出该配合物的标准摩尔生成焓为?fHms=-(2069.30±0.74)kJ·mol-1.     

无水烟酸锂的合成、结构表征及热化学性质

选择分析纯烟酸和一水氢氧化锂为反应物, 利用水热合成方法合成了无水烟酸锂. 利用FTIR和X射线粉末衍射等方法表征了它的结构. 用精密自动绝热热量计测定了它在78～400 K温区的低温热容, 将该温区的摩尔热容实验值用最小二乘法拟合, 得到热容随温度变化的多项式方程. 用此方程进行数值积分, 得到温区内每隔5 K的舒平热容值和相对于298.15 K时的各种热力学函数值. 在此基础上, 通过设计合理的热化学循环, 利用等温环境溶解-反应热量计分别测定该反应的反应物和生成物在所选溶剂中的溶解焓, 从而得到此反应的反应焓为: ＝－(20.21±0.41) kJ• mol－1. 最后, 依据Hess定律计算出无水烟酸锂的标准摩尔生成焓为: [Li(C6H4NO2), s]＝－(278.29±1.01) kJ•mol－1.     

硝基苯与正十六烷在临界区域的液-液共存曲线

用折射率法在离临界温度10.5K范围内测定了硝基苯+正十六烷的温度-折射率(T, n)共存曲线, 通过标准曲线法转化得到温度-摩尔分数(T, x)和温度-体积分数(T, φ)共存曲线, 进而求得临界指数, 与理论值一致。分析实验数据, 给出描述三条共存曲线的方程, 并讨论了选定的序参量的有效性。     

氨基酸在氯乙醇水溶液中的体积性质

利用精密数字密度计测定了甘氨酸、L-丙氨酸和L-丝氨酸在不同质量分数的氯乙醇水溶液中的密度，计算了这些氨基酸在氯乙醇水溶液中的表观摩尔体积、极限偏摩尔体积、迁移偏摩尔体积、理论水化数和体积作用系数，讨论了迁移偏摩尔体积和理论水化数的变化规律. 结果表明，三种氨基酸在氯乙醇水溶液中的迁移偏摩尔体积均为正值, 且随氯乙醇浓度的增大而增大. 氨基酸侧链对迁移偏摩尔体积的贡献与侧链性质密切相关. 三种氨基酸在氯乙醇水溶液中的理论水化数均随溶液中氯乙醇浓度的增加而减小. 甘氨酸与氯乙醇分子间的相互作用主要以1 : 1和1 : 2形式为主， L-丙氨酸和L-丝氨酸与氯乙醇分子间的相互作用主要以1 : 1形式为主.     

298.15 K下氨基酸在D-木糖水溶液中的体积性质

报道了甘氨酸、L-丙氨酸和L-丝氨酸3种典型氨基酸在D-木糖水溶液中的体积性质.     

Excess molar volume and isentropic compressibility of monoethanolamine in aqueous system at temperatures from 298.15 to 318.15 K

Densities and sound velocities for aqueous monoethanolamine (MEA) system are reported over the entire composition range at different temperatures (298.15, 303.15, 313.15 and 318.15 K). These experimental data have been further used in calculating the excess molar volume, partial molar volumes, isobaric thermal expansion coefficients and the deviation in isentropic compressibility. The excess molar volumes data were fitted to the Redlich–Kister polynomial equation to obtain their coefficients and standard deviations. The partial molar volume at infinite dilution of both water in MEA and MEA in water and have been determined using two different methods. Knowledge of the above properties of these mixtures is a basis for understanding some of the molecular interactions in these systems. From the analysis of the results, the type of interactions between the MEA and water is discussed in terms of the number and size of the alkyl groups attached to the nitrogen atom of MEA.     

Volumetric properties of ethanol–water mixtures under high temperatures and pressures

The densities of ethanol and ethanol–water mixtures were measured with a vibrating tube densimeter at 25.0, 50.0 and 75.0 °C in the pressure range from 0.10 to 40.00 MPa. Densities were correlated using an empirical model. Partial molar volumes, excess molar volumes, isothermal compressibilities, cubic expansion coefficients and internal pressures were calculated from obtained densities. This study reports the dependence of densities, partial molar volumes, excess molar volumes, isothermal compressibilities, cubic expansion coefficients and internal pressures on composition, temperature and pressure.     

Effect of Molecular Size of Solutes on Their Partial Molar Volumes in Supercritical n-Pentane

Supercritical fluids (SCFs) have many unique properties1. However, nearly all of the features are related with the aggregation or clustering of the molecules in the fluids. Some researchers have reported that the partial molar volumes (PMVs) of the solutes in dilute supercritical (SC) solutions are large negative values1-4, which is different from common liquid solutions. Negative PMV of a solute in SC solution results from the fact that the local density of the solvent surrounding the so…     

Experimental Vapor Pressures and Derived Thermodynamic Properties of Aqueous Solutions of Lithium Nitrate from 423 to 623 K

Vapor pressures of six aqueous lithium nitrate solutions with molalities of (0.181, 0.526, 0.963, 1.730, 2.990, and 5.250) mol-kg^–1 have been measured in the temperature range 423.15–623.15 K with a constant-volume piezometer immersed in a precision liquid thermostat. The static method was used to measure the vapor pressure. The total uncertainty of the temperature, pressure and composition measurements were estimated to be less than 15 mK, 0.2%, and 0.014%, respectively. The vapor pressures of pure water were measured with the same apparatus and procedure to confirm the accuracy of the method used for aqueous lithium nitrate solutions. The results for pure water were compared with high-accuracy P_S–T_S data calculated from the IAPWS standard equation of state. Important thermodynamic functions (activities of water and lithium nitrate, partial molar volumes, osmotic coefficient, excess relative partial molar entropy, and relative partial molar enthalpy values of the solvent) were derived using the measured values of vapor pressure for the solution and pure water. The measured and derived thermodynamic properties for solutions were compared with data reported in the literature. The present results are consistent with most previous reported thermodynamic data for the pure water and H₂O + LiNO₃ solutions at low temperatures.     

NaCl、KCl在蔗糖水溶液中的粘度

报导了在298．15及308．15K下，NaCl、KCl在含有蔗糖5，10，15，20，25％（质量分数w）的水溶液中的密度及粘度数据．计算了在无限稀释条件下，NaCl和KCl在该体系中的粘度B系数及偏摩尔体积．结果发现：两种电解质的B系数随蔗糖含量的增加及温度的升高而增大且对蔗糖水溶液的结构起破坏作用．讨论了该三元体系内部溶质－溶质、溶质－溶剂间的相互作用，同时应用流动过渡状态理论计算了两种电解质在各组成下蔗糖水溶液中的流动活化参数     

The Partial Molar Volume and Heat Capacity of the Glycyl Group in Aqueous Solution at 25^C

The partial molar volumes, V₂ ^{^}, and the partial molar heat capacities, C_p,2 ^{^}, at infinite dilution have been determined for three new peptides of sequence seryl(glycyl)_xglycine, where x=0 to 2, in aqueous solution at 25^{^}C. Values for V₂ ^{^} at 25^°C have also been determined for two neutral peptide derivatives N-acetylglycylglycinamide and N-acetylglycylglycylglycinamide. These V₂ ^°; and C_p,2 ^°; results were used to estimate the partial molar volume and heat capacity of the backbone glycyl group, CH₂CONH, of proteins in aqueous solution at 25^°;C. The results obtained are compared with those calculated using partial molar data for alternative model compounds. The new glycyl group contributions are in excellent agreement with those currently used in our group additivity schemes for the calculation of the partial molar volumes and heat capacities of unfolded proteins.     

正己烷在乙醇,乙醇—水混合物中的偏摩尔体积

汽油与醇混合物作为动力燃料已日益广泛。为了研究醇中杂质水对这种新型动力燃料有关热力学性质的影响,Letcher等测定了正庚烷-水-醇类三元体系的液-液平衡状态。本文报道C_6H_(14)-C_2H_5OH和C_6H_(14)-C_2H_5OH-H_2O混合物在303.15K的密度,并由此算得正已烷的表观摩尔体积和偏摩尔体积。     

288.15, 298.15和308.15 K温度条件下甘氨酰甘氨酸在蔗糖-水混合溶剂中的体积性质研究

利用Anton Paar DMA55精密数字密度计测定了288.15, 298.15和308.15 K甘氨酰甘氨酸在蔗糖-水混合溶剂中的密度, 计算了甘氨酰甘氨酸的表观摩尔体积VΦ和极限偏摩尔体积 , 得到了其由纯水溶剂转移至混合溶剂中的迁移偏摩尔体积Δtrs 和理论水化数Nh．根据共球交盖模型, 讨论了迁移偏摩尔体积和水化数的变化规律．结果表明, 甘氨酰甘氨酸带电中心与蔗糖之间的结构相互作用对其迁移体积有正贡献, 且占主导地位．甘氨酰甘氨酸的迁移偏摩尔体积为正值, 且随着蔗糖浓度的增大而增大; 理论水化数随温度升高、蔗糖浓度的增大而减小; 温度升高, 极限偏摩尔体积增大, 迁移偏摩尔体积变化很小．