氯化锂溶液表面蒸汽压的理论及实验研究

应用经典热力学理论建立了溶液表面蒸汽压的计算模型,获得了氯化锂溶液的表面蒸汽压随温度及浓度的变化规律;建立了氯化锂溶液表面蒸汽压测量实验台,实验测量结果与理论模型完全符合,验证了本文结果的正确性.     

紫外分光光度法研究β-环糊精与甲基橙的包结行为

利用甲基橙(MO)的吸光度随β-环糊精(β-CD)浓度的增加呈规律性的减弱,而最大吸收波长不变的性质,考察了温度、甲醇浓度、离子强度对其包结平衡常数的影响,计算得到热力学常数并讨论了包结过程的驱动力及可能的包结物结构。结果显示,包结平衡常数随温度、甲醇浓度的升高而减小,随离子强度的升高而增大。热力学常数表明整个包结过程是焓、熵联合驱动的过程,其中疏水作用是主要驱动力。     

缓蚀剂在铜表面吸附行为的研究

采用密度泛函理论计算了缓蚀分子苯并三氮唑(BTA)和二巯基噻二唑(DMTD)的全局反应活性和局部反应活性. 采用分子动力学方法模拟了不同含量的BTA和DMTD对其热力学性质的影响. 同时通过腐蚀试验研究了缓蚀剂复配体系的缓蚀效果. 结果表明: 两种缓蚀分子的缓蚀效率关系为BTA小于DMTD, 活性主要集中于N和S原子上, 有多个活性位点, 因此, 缓蚀剂分子平卧式吸附在铜表面; 铜表面吸附单个缓蚀剂分子BTA和DMTD后, 室温下比热容基本相同, 但随缓蚀剂含量的增加, 比热容呈增大趋势. 这为铜箔轧制油缓蚀剂的选择提供理论指导. 通过腐蚀试验研究, 复配体系缓蚀具有很好的缓蚀效果, BTA和DMTD 的复配比例为1:1时最佳. 关键词： 密度泛函理论 分子动力学方法 反应活性 热力学性质     

固态热容激光器3维瞬态热畸变模拟分析

 根据固态热容激光器的动态工作特性,考虑热力学参数与温度的关系,采用3维有限差分方法模拟分析了薄片热容激光器的3维温度和热应力分布随时间的变化关系。计算了热容激光器的热畸变和退偏损耗随时间的动态变化规律,并与采用连续水冷却方式工作的圆棒激光器的热畸变特性做了比较。模拟结果显示,形变是引起波前相位畸变的主要因素,退偏损耗随泵浦时间增加和泵浦功率增大而非线性增大。     

高压下Ni_3Al热力学性质的第一性原理研究北大核心CSCD

运用第一性原理方法结合准谐Debye-Grüneisen模型研究了高压下Ni3Al的热力学性质,拟合了Ni3Al的状态方程,计算了不同压强下Ni3Al的弹性模量及吉布斯自由能等热力学性质随温度的变化关系.计算结果表明:采用七阶Birch-Murnaghan方程拟合的晶格常数与实验测量结果吻合较好;零压下弹性模量、吉布斯自由能、焓、熵、热容和体膨胀系数随温度的变化与实验值符合较好;在特定压强下,Ni3Al的弹性模量和吉布斯自由能随温度升高而减小,焓、熵随温度升高而增加;预测的德拜温度约为500K,与实验值符合较好.     

氩-碳-硅等离子体热力学性质和输运系数计算

计算了广温度范围(300—30000 K)和广压力范围(0.1—10 atm, 1 atm=101.325 k Pa)下,不同混合物比例、碳和硅蒸气浓度的局域热力学平衡(LTE)和化学平衡(LCE)的氩-碳-硅等离子体组分、热力学性质和输运系数.等离子体气相平衡组分使用质量作用定律计算,同时凝聚相组分采用相平衡的方法计算.输运系数的计算包括黏度、电导率和热导率,使用拓展到高阶近似的Chapman-Enskog方法.采用文献中较新的数据得到了较为准确的碰撞积分,导出了Ar-C-Si等离子体的输运系数.结果表明,在相变温度以下,凝聚态物种的引入导致Ar-C-Si等离子体的热力学性质、输运系数与纯Ar等离子体接近,在相变温度点则会产生不连续点.压力、碳/硅蒸气浓度和比例对等离子体热力学性质和输运系数具有较大影响.最终计算值与文献数据对比符合良好,有望为氩-碳-硅等离子体传热流动数值模拟提供基础数据.     

高压下Ni3Al热力学性质的第一性原理研究

运用第一性原理方法结合准谐Debye-Grüneisen模型研究了高压下Ni3Al的热力学性质,拟合了Ni3Al的状态方程,计算了不同压强下Ni3Al的弹性模量及吉布斯自由能等热力学性质随温度的变化关系. 计算结果表明：采用七阶Birch-Murnaghan方程拟合的晶格常数与实验测量结果吻合较好;零压下弹性模量、吉布斯自由能、焓、熵、热容和体膨胀系数随温度的变化与实验值符合较好;在特定压强下,Ni3Al的弹性模量和吉布斯自由能随温度升高而减小,焓、熵随温度升高而增加;预测的德拜温度约为500K,与实验值符合较好.     

Zn含量对重电子金属CeCu6-xZnx低温性质的影响

报道了掺Zn的重电子金属CeCu6-xZnx(x=0.05,0.1,0.15,0.2,0.3)样品的非常规制备方法以及低温电阻和低温比热容的测量结果,研究Zn含量对CeCu6-xZnx低温性质的影响及其物理原因.发现低温下Kondo散射项系数c随Zn含量的加大而减小,电阻极大值温度Tmax随Zn含量的加大而降低,CeCu6-xZnx的德拜温度ΘD随Zn含量的加大而略有上升 关键词： 重费密子系统 低温比热容 低温电阻 相干散射     

流化床生物质快速热解制取生物油试验研究

本文在小型流化床试验装置中对颗粒状的樟子松进行制取生物油的试验研究.考察了反应温度对热解生物油物理性质和产率的影响,并重点研究了各个参数对热解生物油组分的影响规律.结果表明,在550℃下生物油产率最高,为50.4%(w/w).随着热裂解温度升高,生物油的密度略有增加,生物油的粘度随着含水率的增加而减小.反应温度对生物油的主要化学成分和含量影响不明显,生物油主要含有有机酸类、酚类和糖类等化合物.     

外场作用下铁电/铁磁双层膜的极化磁化性质

建立了铁电/铁磁双层膜模型,铁电层的电矩用连续标量描述,而铁磁层的自旋应用经典矢量描述.利用蒙特卡罗方法模拟了体系的热力学性质和极化、磁化行为.给出了零场下体系的内能、比热、极化和磁化随温度变化的关系,并分别研究了体系在外磁场和外电场下的极化和磁化行为.模拟结果表明,双层膜体系的内能、比热、极化和磁化性质因层间耦合系数的不同而明显不同,当界面耦合较弱时,双层膜表现出各自的热力学性质,当层间耦合增强到一定程度时,双层膜耦合为一个整体,表现出统一的热力学性质.该双层膜在外场中形成电滞回线和磁滞回线,并表现出偏置特性,界面耦合强度和温度影响滞后回线和偏置现象.     

苯的硝基和叠氮基衍生物热力学性质的构效关系

苯的硝基和叠氮基衍生物是一类重要的含能材料,为了揭示其热力学性质与分子结构之间的关系,采用第一性原理进行了计算研究.通过计算平衡电负性连接指数,结合分子结构描述符,对苯的硝基和叠氮基衍生物的热力学性质建立了构效关系模型.模型检验结果表明,构建的模型具有良好的稳健性和预测能力,所得模型为苯的硝基和叠氮基衍生物的爆轰参数计算和分解机理研究提供了一种快速的热力学性质预测方法 .     

苯的硝基和叠氮基衍生物热力学性质的构效关系

苯的硝基和叠氮基衍生物是一类重要的含能材料,为了揭示其热力学性质与分子结构之间的关系,采用第一性原理进行了计算研究。通过计算平衡电负性连接指数,结合分子结构描述符,对苯的硝基和叠氮基衍生物的热力学性质建立了构效关系模型。模型检验结果表明,构建的模型具有良好的稳健性和预测能力,所得模型为苯的硝基和叠氮基衍生物的爆轰参数计算和分解机理研究提供了一种快速的热力学性质预测方法。     

流体混合物热力学性质计算的混合法则新进展

回顾近期关于流体混合物热物性混合法则的研究新进展,特别是余吉布斯自由能(GE)和余亥姆霍兹自由能(AE)型混合法则的拓展及应用,重点介绍一种基于AE,仅通过偏微分方程便可计算混合物所有热力学性质的混合法则。可为发展未知流体混合物热物性计算方法以及各种常见混合物热物性的工程应用提供参考和依据。     

Multicanonical sampling of the space of states of ℋ(2, <Emphasis Type="Italic">n</Emphasis>)-vector models

Problems of temperature behavior of specific heat are solved by the entropy simulation method for Ising models on a simple square lattice and a square spin ice (SSI) lattice with nearest neighbor interaction, models of hexagonal lattices with short-range (SR) dipole interaction, as well as with long-range (LR) dipole interaction and free boundary conditions, and models of spin quasilattices with finite interaction radius. It is established that systems of a finite number of Ising spins with LR dipole interaction can have unusual thermodynamic properties characterized by several specific-heat peaks in the absence of an external magnetic field. For a parallel multicanonical sampling method, optimal schemes are found empirically for partitioning the space of states into energy bands for Ising and SSI models, methods of concatenation and renormalization of histograms are discussed, and a flatness criterion of histograms is proposed. It is established that there is no phase transition in a model with nearest neighbor interaction on a hexagonal lattice, while the temperature behavior of specific heat exhibits singularity in the same model, in case of LR interaction. A spin quasilattice is found that exhibits a nonzero value of residual entropy.     

Microscopic systems with and without Coulomb interaction, fragmentation and phase transitions in finite nuclei

We test the influence of the Coulomb interaction on the thermodynamic and cluster generation properties of a system of classical particles described by different lattice models. Numerical simulations show that the Coulomb interaction produces essentially a shift in temperature of quantities like the specific heat but not qualitative changes. We also consider a cellular model. The thermodynamic properties of the system are qualitatively unaltered. Received: 7 November 2000 / Accepted: 17 May 2001     

First-principles calculations of structural and thermodynamic properties of β-PbO

We employed ab-initio calculations to investigate the structural and thermodynamic properties of Massicot or orthorhombic phase of PbO named β-PbO using the projector augmented-wave(PAW) method within the generalized gradient approximation(GGA). The temperature and pressure dependence of bulk modulus, heat capacity at constant pressure and constant volume, entropy, thermal expansion coefficient and Grüneisen parameter were discussed. Accuracy of two different models, the Debye and Debye-Grüneisen which are based on the quasi-harmonic approximation(QHA) for producing thermodynamic properties of material were compared. According to calculation results, these two models can be used to designate thermodynamic properties for β-PbO with sensible accuracy over a wide range of temperatures and pressures, and our work on the properties of this structure will be useful for more deeply understanding various properties of this structure.     

Vapour–liquid equilibrium of fluids composed by oblate molecules

Gibbs ensemble Monte Carlo simulations are performed to obtain the vapour–liquid equilibrium of oblate-like fluids interacting through the Kihara intermolecular potential. Results confirm the validity of a perturbation theory for Kihara fluids, whose accuracy for prolate fluids was tested some years ago. As in the case of hard ellipsoids, the symmetry of the phase diagram of oblate and prolate models is analysed. An interesting relation of Boyle temperature and critical parameters with molecular volume is found for the considered models. As a particular application, this relation allows the prediction of some thermodynamic properties of a new promising biofuel 2,5dimethylfuran.     

Thermodynamic properties of inhomogeneous fluids

A general method, the method of variation under extension, is presented for expressing the thermodynamic properties of an inhomogeneous fluid as functionals of the local number density, when given a density functional for the total thermodynamic grand potential of the fluid. The method is demonstrated in detail for the van der Waals square-gradient density functional and for the nonlocal density functional which arises in the theory of fluids with long-ranged pair potentials or in the mean-field theory of penetrable-sphere models. As specific examples, we consider the planar and spherical interface between two fluid phases, the line of contact of three fluid phases, the contact line between two surface phases and the planar interface between a solid and fluid.     

Mg2Sn电子结构及热力学性质的第一性原理计算

采用基于第一性原理的赝势平面波方法系统地计算了Mg₂Sn基态的电子结构、弹性常数和热力学性质.计算结果表明Mg₂Sn的禁带宽度为0.1198eV.运用线性响应方法确定了声子色散关系和态密度,得出Mg₂Sn的热力学性质如等容比热和德拜温度.计算Mg₂Sn的热导率并与实验数据相比较. 关键词： 第一性原理 电子结构 弹性常数 热力学性质     

Free energies of ionic nanoclusters. Solid and coexistent solid-liquid states

A strategy to overcome some specific problems associated to the computation of free energies in clusters is presented. Free energies and entropies of solid KCl nanoclusters are determined by thermodynamic integration, and Watanabe and Reinhardt’s dynamical method, based on molecular dynamics simulations. The values are in good agreement with experimental data. From a previous theoretical prediction of the caloric curve, T(E), for the coexistence region, an equation is derived to compute the free energies of the clusters at the solid-liquid coexistence. The results are discussed in the context of the thermodynamic stability of phase coexistent states for finite and infinite systems, yielding consistent conclusions.