二氧化碳-甲苯体系的气-液平衡研究

采用了改进的Novak和Conway气体溶解度实验装置,在低压下测定了298.15K,303.15K和316.15K时二氧化碳在甲苯中的溶解度,回归得到了常压下Henry常数与温度的关联式。借助于实测的溶解度数据,求得了不同温度下P-R方程中的二元作用参数δ_(12),推算了不同温度下,该体系的高压气-液平衡数据,温度范围从298K到477K,压力从常压下推算到15.3MPa。推算值与文献值的一致,说明我们的实验数据和从已知温度、总压推算二元系x、y的方法是合理的。同时,用R-R方程计算了CO_2在C_(?)H_(?)CH_3中的偏摩尔体积。     

含醇二元体系热力学性质的研究 Ⅱ.C_1～C_5正链醇+1,4-二氧六圜的过量焓

本工作利用Picker混合型流动微量量热器测量了298.15K时,1,4-二氧六圜+甲醇,+乙醇,+正丙醇,+正丁醇和+正戊醇的摩尔过量焓。仪器以苯+环已烷和苯+四氯化碳两个体系校验,x=0.5时的混合热数值,与文献值相符在1％以内。试剂按常规方法处理,纯化液体的折光率,与文献值一致。将测得各体系的摩尔过量焓,拟合为如下的多项式:     

α-蒎烯+对伞花烃和β-蒎烯+对伞花烃二元体系超额焓的测定

采用BT2.15型Calvet微量量热计常压下测定了α-蒎烯+对伞花烃和β-蒎烯+对伞花烃两个二元体系在298.15 K、308.15 K及318.15 K下的超额焓. 实验数据采用Redlich-Kister方程进行关联, 标准偏差较小. 该两个二元体系的超额焓在全浓度范围内均为正值, 其最大值在摩尔分数x1=0.5附近. 温度对超额焓有一定的影响, 超额焓随温度的升高而增大. 相同温度下, α-蒎烯+对伞花烃体系的超额焓比β-蒎烯+对伞花烃体系的大.     

正烷醇/异丙醇二元体系过量焓的测定

用LKB 2277 Bioactivity Monitor测定了一些正烷醇(甲醇到正己醇)与异丙醇二元体系在298.15K的常压过量焓H^E的数据, 对丙醇/异丙醇, 正丁醇/异丙醇和正戊醇/异丙醇还测定了308.15K和313.15K的常压过量焓数据。同时给出了关联实验结果的多项式方程的各参数。     

1-丁基-3-甲基咪唑四氟硼酸盐的热稳定性、平衡蒸汽压和标准蒸发焓

利用非等温、等温热重分析(TG)法,研究了高纯氮气气氛下1-丁基-3-甲基咪唑四氟硼酸盐([bmim][BF4])离子液体的热稳定性、平衡蒸汽压和标准蒸发焓.非等温热重(TG)曲线表明[bmim][BF4]的初始分解温度(Tonset)和最大分解速率对应的温度(Tm)分别为697和734K.然而长期等温TGA研究表明,[bmim][BF4]的最高可使用温度约为513K.另外,利用基于TG的蒸发技术研究了[bmim][BF4]的平衡蒸汽压(pe)与温度的关系并计算了标准蒸发焓.在503-543K温度范围内,离子液体[bmim][BF4]的pe和温度的关系是:lgpe=(16±1)+(-6.85±0.25)×103/T.[bmim][BF4]的标准蒸发焓为(131±5)kJ·mol-1.     

稀土高氯酸盐-甘氨酸配合物[Sm2(Gly)6(H2O)4](ClO4)6.5H2O单晶体的低温热容及标准生成焓

合成了稀土高氯酸盐-甘氨酸配合物晶体。经热重、差热、化学化析及有关文献对比,确定其组成是[Sm2(Gly)6(H2O)4](ClO4)6·5H2O,单晶结构,纯度是99.0%.熔点分析仪分析知其没有固定熔点,在79～370K温区,用高精密全自动绝热量仪对单晶配合物进行了热容测定,发现该配合物在低温段没有反常热容。348.07K附近是该配合物的分解温区,配合物的分解温度、分解熵和分解焓分别是346.89K,44.669kJ/mol和128.77J/K·mol。计算机拟合了热容对温度的多项式方程,在79～318K温区,Cp=1294.56+624.17K-11.893X^2+75.075X^3+23.762X^4.在常压,298.15K下用具有恒温环境的反应热量计测定了配合物的标准生成焓值为-8022.405kJ/mol。     

稀土高氯酸盐-甘氨酸配合物[Sm2(Gly)6(H2O)4](ClO4)6·5H2O单晶 体的低温热 容及标准生成焓

合成了稀土高氯酸盐-甘氨酸配合物晶体。经热重、差热、化学化析及有关文献对比,确定其组成是[Sm2(Gly)6(H2O)4](ClO4)6·5H2O,单晶结构,纯度是99.0%.熔点分析仪分析知其没有固定熔点,在79～370K温区,用高精密全自动绝热量仪对单晶配合物进行了热容测定,发现该配合物在低温段没有反常热容。348.07K附近是该配合物的分解温区,配合物的分解温度、分解熵和分解焓分别是346.89K,44.669kJ/mol和128.77J/K·mol。计算机拟合了热容对温度的多项式方程,在79～318K温区,Cp=1294.56+624.17K-11.893X^2+75.075X^3+23.762X^4.在常压,298.15K下用具有恒温环境的反应热量计测定了配合物的标准生成焓值为-8022.405kJ/mol。     

4-羟甲基吡啶的热力学性质

用精密自动绝热量热计测定了4-羟甲基吡啶在79～380 K温区的摩尔热容. 实验结果表明, 该化合物在79～301 K温区无相变和热异常现象发生, 在301～331 K, 发生固-液相变, 其熔化温度、摩尔熔化焓及摩尔熔化熵分别确定为：325.12 K, 11.78 kJ•mol^-1 和36.23 J•K^-1•mol^-1. 根据热力学函数关系式, 从热容值计算了4-羟甲基吡啶在80～380 K温区以标准状态（298.15 K）为基准的热力学函数值. 用热重法(TG)对该化合物的热稳定性作进一步考察, 从TG曲线上观察到该化合物在490 K有最大的蒸发失重速率.     

基于Barton-Zard反应的2-乙氧羰基-3-三氟甲基-4-甲基吡咯及其卟啉衍生物的改进合成

由2-乙氧羰基-3-硝基-1,1,1-三氟丁烷(1b)与异氰基乙酸乙酯发生Barton-Zard反应制备2-乙氧羰基-3-三氟甲基-4-甲基吡咯(1)的过程中,分别用K2CO3和乙醇代替有机碱1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)和四氢呋喃溶剂,这种改进的Barton-Zard方法具有操作简便、试剂价廉易得、溶剂毒性低和产率更高等优点。 另外,在3-硝基-1,1,1-三氟-2-丁醇(1a)通过乙酰化反应转变为中间体1b的过程中,用沸腾温度下的甲苯溶液与乙酰氯代替浓硫酸催化下的酸酐反应体系;合成化合物1b的最优化的反应条件被确定为：乙酰氯与反应物1a之间的摩尔比为1.2∶1,反应时间为3～3.5 h。 又根据改进的卟啉合成法,在低温下用过量氢化铝锂还原吡咯1,将还原所得的尚未干燥或储存的粗产物α-羟甲基-三氟甲基-4-甲基吡咯(1c),立即在未经处理的三氯甲烷溶剂中,以三氟化硼·乙醚(BF3·OEt2)为催化剂进行四聚化反应,然后用2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)氧化,合成出含三氟甲基取代的卟啉衍生物2。 研究发现,由化合物1c制备产物2时,用BF3·OEt2取代p-TsOH作为催化剂,在确定的反应条件下,能够将产物2的收率由14%提高至50%。     

1-甲基-3,5-二苯基-吡唑的低温热容和热力学性质

通过精密自动绝热热量计测量了自己合成并提纯1-甲基-3,5-二苯基-吡唑在78～370K温区的摩尔热容。实验结果表明,这个化合物有一个固-液熔化相变,其熔化温度、摩尔熔化焓以及摩尔熔化熵分别为：(332.903±0.152)K,(17463.48±21.81)J·mol^-1和(52.55±0.06)J·mol^-1·K^-1。通过分步熔化法得到样品的纯度和绝对纯样品熔点分别为：0.9954(摩尔分数)和333.115K。在热容测量的基础上计算出了该物质每隔5K的热力学函数值。用DSC技术对该物质的固液熔化过程作了进一步研究,结果与热容实验相一致。     

Radiothermoluminescence. II. Radiothermoluminescence of polyethylene with different chain conformations

Molecular relaxation processes in the 77–260°K interval and the structure of polyethylene melt-crystallized under normal and high pressures have been studied. The positions of relaxation transitions and activation energy for molecular relaxation were determined by radiothermoluminescence. The most intense maximum in the glow curve of the sample crystallized under normal pressure is observed in the 200–240°K interval, i.e., in the range of the β transition. In this temperature interval the β relaxation activation energy changes from 15 to 25 kcal/mole. An increase of the pressure under which crystallization takes place results in a substantial decrease of the intensity of the β maximum. This indicates that the β transition of polyethylene is most probably due to the mobility of segments on the chain-folded lamellar surface. For samples melt-crystallized under pressure between 5000 and 7000 atm, relaxation transitions were found at 150 and 190°K. Various processes of molecular relaxation appear to be associated with the maxima observed on the polyethylene glow curve.     

Thermodynamics of liquid-gas phase equilibria in the dipropylsulfoxide-water system in the range of 303.15 to 323.15 K

The saturation vapor pressure of pure dipropylsulfoxide (DPSO) is measured in the temperature range of 303.15 to 323.15 K. The boiling point of DPSO under normal pressure (479.15 K) is determined and the molar heat of vaporization of DPSO is calculated (Δ_v H ^○ = 61.4 ± 3.1 kJ/mol) on the basis of data obtained via graphical extrapolation. The total saturation vapor pressure of aqueous solutions of DPSO of various concentrations at 303.15 and 308.15 K is measured. Partial pressures, the activity coefficients of DPSO and H₂O, and the excess Gibbs energy of mixing are calculated on the basis of the obtained results.     

燃料馏分油气－液相平衡常数的测定与关联

实沸点蒸馏原油获得燃料馏分油。采用拟静态法测定不同沸程的22种燃料馏分油在系列温度下的泡点蒸气压，用Antoine方程关联蒸气压与温度的关系。在泡点压力分别为10 kPa、30 kPa、50 kPa、80 kPa和101.325 kPa时，按虚拟组分处理法计算了燃料宽馏分油中各虚拟组分的气-液相平衡常数，关联了气-液相平衡常数与虚拟组分的沸点以及相平衡温度、压力的关系，得到的表达式可以计算常压沸点范围在348.15 K至623.15 K间燃料宽馏分油的气-液相平衡常数，经180个数据点回归检验，平均误差为4.5%。     

Does SDS micellize under methane hydrate-forming conditions below the normal Krafft point?

Sodium dodecyl sulfate (SDS) can accelerate nucleation and growth of gas hydrates in a quiescent system. The objective of this paper is to investigate whether or not SDS micelles form in the meta-stable region of methane hydrates by the direct measurement of aqueous SDS concentration. The SDS solubility in water with high-pressure methane is identical to that under atmospheric pressure at a temperature range of 270-282 K; thus, the Krafft point under these methane hydrate-forming conditions does not shift from the normal Krafft point (281-289 K) under atmospheric pressure. The mole fraction of methane in SDS solution is independent of aqueous SDS concentration at a hydrate-forming condition. These results suggest that at temperatures below the normal Krafft point, no SDS micelles are present in the aqueous phase even in a high-pressure methane environment.     

Thermodynamic properties of three adamantanols in the ideal gas state

The enthalpies of sublimation and the saturated vapor pressure of 1-adamantanol (1-Adol), 2-adamantanol (2-Adol) and 2-methyl-2-adamantanol (2-Me-2-Adol) were measured. Thermodynamic functions of the compounds under study in the ideal gas state between 100 and 1000 K were calculated by the statistical thermodynamic methods. The sets of wave numbers of normal vibrations for adamantanols were obtained by semi empirical calculation (MINDO3 И MNDO/d). The experimental entropies for gaseous adamantanols and the calculated values were in the satisfactory agreement.     

The effect of temperature and pressure on acoustic and thermodynamic properties of 1,4-butanediol. The comparison with 1,2-, and 1,3-butanediols

The speeds of sound in 1,4-butanediol have been measured in the temperature range from (298 to 318) K at pressures up to 101 MPa by the pulse-echo-overlap method. The densities have been measured in the temperature range from (293.15 to 353.15) K under atmospheric pressure with a vibrating tube densimeter. Based on the experimental results, the densities, isobaric heat capacities, isobaric coefficients of thermal expansion, isentropic and isothermal compressibilities, as well as the internal pressure as function of temperature and pressure have been calculated. The effects of pressure and temperature are discussed and compared with the previous results for 1,2- and 1,3-butanediols.     

Solubility and thermodynamic properties of acetaminophen in 1-hexyl-4-methylpyridinium bromide and water mixtures

The solubility data of acetaminophen in binary mixtures of 1-hexyl-4-methylpyridinium bromide and water were obtained over the temperature range from 293.15 to 313.15 K by using the gravimetric method under atmospheric pressure. Using the experimentally measured solubility values, the thermodynamic properties of dissolution, mixing and transfer processes were evaluated. The measured solubilities were correlated by the modified Wilson and the electrolyte non-random two liquid (E-NRTL) models.     

氢在活性炭、石墨烯和金属有机骨架上的吸附平衡

为比较不同物理吸附材料的结构参数对其储氢性能的影响,制备和选取了具有超高比表面积的活性炭、石墨烯以及金属有机骨架（MOFs）作为低温吸附储氢的典型材料。首先,利用77 K下氮气在材料上的吸附数据确定了其BET比表面积以及孔径分布的主要结构参数。其次,利用3Flex全自动微孔吸附仪在77-87 K测试了0-0.1 MPa低压下氢在各材料上的吸附量,而后在0.1-8 MPa高压条件下利用PCTPro测试了氢在各材料上的过剩吸附量。最后,分析了各材料的储氢量与其结构参数间的关系。结果表明,在低压下,影响物理吸附材料储氢量的主要因素为孔径分布小于1 nm的微孔;而高压下,氢在多孔材料上的最大过剩吸附量与材料的BET比表面积呈正相关关系,斜率为0.0059 mmol/m²。     

Pression De Vapeur Et Decomposition Thermique De La Monomethylhydrazine

Monomethylhydrazine (MMH) (CH₃)NHNH₂ is currently used as fuel for spacecraft engine combustion chambers. The Aestus engine of the upper stage of Ariane 5 is fed with MMH under pressure of 16 bars. The propellant, initially at room temperature, is about 393 K when introduced into the combustion chamber, due to heating up through the regenerative circuit. As MMH is unstable above 373 K, it has been necessary to check its decomposition rate and vapor pressure under such conditions. The vapor pressure of this propellant has been measured in a pressure vessel and the thermal decomposition rate was determined with the same device up to 500 K. This revised version was published online in August 2006 with corrections to the Cover Date.     

Experimental and modeling studies on the asphaltene precipitation in degassed and gas-injected reservoir oils

The asphaltene precipitation in a Chinese crude oil has been studied experimentally under normal-pressure and high-pressure conditions. The onset of asphaltene precipitation was detected by using light transmission method. Normal pentane and hexane were used as precipitating agents for studying the onset of asphaltene deposition in (asphaltene+toluene) and (degassed crude oil+toluene) mixtures under normal pressure. A total of eighteen sets of normal pressure data have been measured. For high-pressure gas-injected reservoir oil systems, the effects of injection-gas concentration, temperature, pressure, and the presence of a coexisting aqueous electrolyte (brine) phase on the amount of asphaltene deposition were studied and a total of seven sets of data have been measured. In the modeling part, a modified Hirschberg solubility model and a new solubility parameter correlation were proposed. The model parameters determined from low-pressure precipitation data have been successfully extended to high-pressure systems. Extensive tests vs. the data measured in this work and literature data show that the proposed model is capable of giving reasonable calculation results for most cases.