混合电解质NaBr+NaAc十H_2O体系的活度系数的测定

用电势法测定了298.15K以及I为0.1、0.5、1.0、1.5、2.0、2.5和3.0 mol/kg时,NaBr在混合电解质溶液NaBr+NaAc+H_2O中的活度系数.实验结果用Harned、SRJ和Pitzer方程拟合,得到各种方程的相互作用参数,由拟合的标准偏差得知,Pitzer方程的拟合精度略好于前2个方程.用Pitzer混合参数θ_(Br-Ac)和ψ_(Br-Na-Ac)计算了NaAc在该混合体系中的活度系数和体系的过量Gibbs自由能.     

混合电解质NaBr+NaAc十H_2O体系的活度系数的测定

用电势法测定了298.15K以及I为0.1、0.5、1.0、1.5、2.0、2.5和3.0 mol/kg时,NaBr在混合电解质溶液NaBr+NaAc+H_2O中的活度系数.实验结果用Harned、SRJ和Pitzer方程拟合,得到各种方程的相互作用参数,由拟合的标准偏差得知,Pitzer方程的拟合精度略好于前2个方程.用Pitzer混合参数θ_(Br-Ac)和ψ_(Br-Na-Ac)计算了NaAc在该混合体系中的活度系数和体系的过量Gibbs自由能.     

平均球近似法计算电解质活度系数的研究(Ⅱ)——混合电解质水溶液

用(I)报中所得到的阳离子有效直径参数,用平均球近似(MSA)法,在不用混合参数的条件下,预测了32个混合电解质水溶液的离子平均活度系教.预测的Inγ_± 与实验值的平均标准偏差为0.0113.文中还用Pitzer方程作了计算.结果表明本文预测结果比无混合参数的Pitzer方程好得多,接近于带混合参数的Pitzer方程的关联结果,作者还分别预测了各温度下4个混合电解质水溶液饱和浓度时的活度系数,结果令人满意.     

Theoretical calculations of phase equilibrium in interactive quaternary system Na + , K + //Br- , SO2-4 -H2 O at 323 K

应用323 K三元子体系的溶解度数据,采用多元线性回归方法拟合出该四元体系在323 K时的Pitzer方程的混合离子相互作用参数θ(Br-,SO2-4),Ψ(Na+,Br-,SO2-4),Ψ(K+,Br-,SO2-4)(相关文献鲜有报道),在此基础上应用Pitzer方程对323 K四元体系Na+,K+∥Br-,SO2-4-H2O的溶解度数据进行理论计算,并用计算出的溶解度数据绘制出四元相图.计算结果表明,模拟计算值与实测值基本吻合,较好地验证了实验数据的准确性,同时也表明含有合理参数的Pitzer模型完全可以描述含Na+,K+∥Br-,SO2-4-H2O的体系.     

交互四元体系Na~+,K~+∥Br~-,SO_4~(2-)-H_2O 323K相平衡理论计算

应用323 K三元子体系的溶解度数据,采用多元线性回归方法拟合出该四元体系在323 K时的Pitzer方程的混合离子相互作用参数θ(Br-,SO24-),Ψ(Na+,Br-,SO24-),Ψ(K+,Br-,SO24-)(相关文献鲜有报道),在此基础上应用Pitzer方程对323 K四元体系Na+,K+∥Br-,SO24--H2O的溶解度数据进行理论计算,并用计算出的溶解度数据绘制出四元相图。计算结果表明,模拟计算值与实测值基本吻合,较好地验证了实验数据的准确性,同时也表明含有合理参数的Pitzer模型完全可以描述含Na+,K+∥Br-,SO24--H2O的体系。     

三元体系KCl–KBr–H_2O 323K相平衡理论计算

根据三元体系KCl–KBr–H_2O相平衡实验数据,回归了该体系中K(Cl,Br)固溶体的组成和平衡液相组成对应的二次方程,对固溶体组成的计算值和实验值进行了对比讨论,计算值的偏差范围在0.36%~3.31%;应用文献报道的Pitzer方程参数与温度的关联方程计算了323 K时该三元体系中盐的Pitzer方程单盐参数,并拟合了该三元体系中固溶体K(Cl,Br)和溴盐关联的活度积。在此基础上应用Pitzer方程和粒子群算法(PSO),对323 K时三元体系KCl–KBr–H_2O的溶解度数据进行理论计算,并用计算出的溶解度数据绘制出该三元体系323 K时的相图,计算结果表明,溶解度的理论计算值与实验值吻合好。     

含盐溶液汽液平衡预测(Ⅰ)——Pitzer模型的扩展及其在多元体系中的应用

本文提出一种新的预测含盐溶液汽液平衡的方法.对Pitzer(1980)模型进行扩展后,将其简化成单参数形式,推广至多元电解质溶液;经过适当假定,得到计算含盐挥发性强电解质和水体系及含盐水醇体系的活度系数公式,这些公式仅含二元相互作用参数;由二元溶液的活度关联出该参数后,可用于含盐体系各种温度下汽液平衡的预测.关联了40个二元电解质水溶液及7个电解质甲醇溶液298.15K时的简化Pitzer方程的单参数;用以推算6个水盐体系和2个甲醇盐体系在320-403K的蒸汽压,得到满意的结果,182个数据点的平均偏差小于0.65kPa;用以预测5个不同类型的含盐三元体系的等温、等压汽液平衡,所得的平均偏差对于汽相组成、沸点、压力分别为0.015、1K和1.92kPa.     

含盐溶液汽液平衡预测(Ⅰ)——Pitzer模型的扩展及其在多元体系中的应用

本文提出一种新的预测含盐溶液汽液平衡的方法.对Pitzer(1980)模型进行扩展后,将其简化成单参数形式,推广至多元电解质溶液;经过适当假定,得到计算含盐挥发性强电解质和水体系及含盐水醇体系的活度系数公式,这些公式仅含二元相互作用参数;由二元溶液的活度关联出该参数后,可用于含盐体系各种温度下汽液平衡的预测.关联了40个二元电解质水溶液及7个电解质甲醇溶液298.15K时的简化Pitzer方程的单参数;用以推算6个水盐体系和2个甲醇盐体系在320-403K的蒸汽压,得到满意的结果,182个数据点的平均偏差小于0.65kPa;用以预测5个不同类型的含盐三元体系的等温、等压汽液平衡,所得的平均偏差对于汽相组成、沸点、压力分别为0.015、1K和1.92kPa.     

钠钙氯化物在乳糖水中热力学性质的确定

在298.15 K时利用电动势法确定四元体系氯化钠-氯化钙-乳糖-水不同组成(乳糖质量分数分别为0,5%,10%和15%)时的热力学性质。利用Pitzer离子作用模型拟合实验数据,获得了氯化钠和氯化钙在乳糖水混合溶剂中的Pitzer模型参数。进一步计算了氯化钠和氯化钙从纯水到乳糖水混合溶剂中的迁移吉布斯函数。获得了氯化钠和氯化钙混合电解质在乳糖水混合溶剂中的混合参数θ(Na Ca)和ψ(Na Ca Cl)。计算了298.15 K时四元体系中氯化钠和氯化钙的平均离子活度系数。结果发现:利用Pitzer高阶静电作用模型计算混合电解质在混合溶剂中的平均离子活度系数,能获得较为满意的结果。     

电动势法确定水-丙酮-氯化钠-氯化镁体系热力学性质

采用自行设计的无液体接界电池测定了多组分电解质在水溶液和混合溶剂中不同组成时电池的电动势.利用Pitzer模型拟合实验数据,获得电池的标准电动势E(○)及电解质的活度系数.此外,计算了电解质从纯水到混合溶剂中的迁移吉布斯函数,求得了Pitzer模型的计算参数.获得了NaCl和MgCl2混合电解质的混合参数θ(NaCl)...     

氯化氢、水、甲醇三元体系汽液平衡的研究(Ⅰ)——氯化氢、水二元体系汽液平衡的测定及关联

用双循环型平衡釜测定了latm下盐酸体系的汽液平衡关系,所得数据与具有代表性的诸文献值作了比较和评价. 将Pitzer(1980年)方程简化成单参数形式,通过关联盐酸中水的活度系数,求得参数,然后推算其中氯化氢的活度系数及汽液平衡数据,结果与本文实测数据相一致,19组沸点的平均偏差为0.046℃、15组汽相组成(摩尔分率)的平均偏差为0.0020.     

4种智能算法在相平衡数据拟合中的应用

针对Marquardt-Levenberg法应用于多元物系相平衡数据拟合时,模型参数剧增,初值难以设定的难题,将4种智能算法,即遗传算法、神经网络,退火算法及粒子群算法,应用于相平衡数据的拟合。以正丙醇（1）+乙腈（2）二元物系汽液相平衡数据的Wilson拟合和甲醇（1）+乙腈（2）+1-乙基-3-甲基咪唑四氟硼酸盐（3）三元物系汽液相平衡数据的NRTL拟合为例,系统讨论了4种算法在应用时的主要影响因素,并将所得结果进行了分析和比较。结果表明遗传算法和粒子群算法可以较好地解决初值难设的问题,并且给出了每种算法的适用范围和使用建议。     

APPLICATION OF THE BRUNAUER- EMMETT-TELLER ISOTHERM TO THE WATER-NITRIC ACID SYSTEM FOR THE DETERMINATION OF MEAN IONIC ACTIVITY COEFFICIENTS

The application of the BET model to determine ionic activity coefficients of the aqueous nitric acid system is investigated. BET parameters are determined from published data and the model is applied to predict activity coefficients up to very high concentrations. It is shown that the BET model can be used on systems where the reference state is not a regular solid crystal and which exhibit strong hydrogen bonding. Additionally, it is demonstrated that the BET model shows a good potential for application at concentrations an order of magnitude higher than previously investigated. It is revealed that the most important parameter in the BET model at very high concentrations is the choice of a reference state. The focus of this ongoing study is outlined.     

Modeling induced nucleation processes during batch cooling crystallization: A sequential parameter determination procedure

An existing model is extended to simulate batch cooling crystallizations with induced nucleation processes like ultrasound or gassing. All important phenomena such as nucleation, growth, agglomeration and breakage are taken into account. A differentiation between ultrasound and gassing is necessary. Induced nucleation processes also require a modification of crystal growth mechanism.In general, the model parameters required for the kinetics are determined simultaneously by fitting them to experimental data. Mostly a correlation model results without physical basis. Here, the model parameters are sequentially determined by decoupling the mechanisms, saving effort and time, and make it possible to reduce the number of parameters also. The model and the model parameter determination procedure are validated using three different organic solute/solvent systems. The number of simulation runs for parameter fitting was reduced to less than 100 instead of simultaneous parameter determination, which requires several hundreds of thousands runs, resulting in physically reasonable solutions.     

逆向法测定酮洛芬对映体在Chiralpak AD柱上的吸附等温线

模拟移动床（SMB）色谱分离与纯化的操作过程复杂,对其进行设计与优化需要使用数值模拟方法,准确测定竞争型吸附等温线具有重要意义。采用逆向法确定了25℃下酮洛芬对映体在直链淀粉手性固定相（Chiralpak AD）上的竞争吸附等温线,先用高效液相色谱测得酮洛芬对映体在Chiralpak AD 柱上的过载流出曲线,再通过拟合实验测得的流出曲线确定吸附等温线模型及其参数。研究中采用平衡扩散模型描述酮洛芬对映体在色谱柱上流出的瞬态过程。参数拟合过程中,首先用非支配基因算法（NSGA-Ⅱ）在较广的参数空间内搜索吸附等温线模型参数,再以所得结果作为初值,使用Levenberg-Marquardt 算法（LMA）对参数进一步优化。比较了4种不同竞争吸附等温线模型对实验测得的流出曲线的拟合结果,其中五参数的Bi-Langmuir 模型拟合程度最好。测量了不同进料浓度和进料量条件下的流出曲线,并通过与模型预测结果的对照验证了所确定吸附等温线模型和参数。     

Modeling on lithium insertion of porous carbon electrodes

MCMBs with different crystal structure were tested for an anode of lithium ion batteries (LIB) and the model describing the behavior of porous anodes was simulated numerically by using orthogonal collocation method (OCM). Kinetic parameters such as diffusion coefficients, exchange current densities, and transfer coefficient, describing electrochemical intercalation system of lithium ions, were estimated by fitting the experimental cyclic voltametry (CV) results with the theoretical ones. It was investigated that the theoretical cyclic voltamograms obtained using above parameters fitted well with the experimental curves for the various scan rates from 1 mV s⁻¹ to 5 μV s⁻¹. The parameters were then evaluated on their extended application in various C-rate-charge/discharge cycling tests with showing good agreements between experiments and simulations. As the results show, it was found that numerical simulations based on both potentiometry and galvanometry experimental data resulted in more accurate parameters of electrochemical system. Simulations indicate there exist the optimum design conditions of electrode and separator to obtain the good performance of lithium ion batteries.     

Dynamic simulation of cyclic voltammogram on the electrochemical reduction of VO2+ ions

An electrochemical reduction of VO²⁺ ions in a formic acid electrolyte was analyzed by cyclic voltammetry. A new four step reaction mechanism, EECE, was proposed to derive the mass transfer equation, and then it was solved by numerical method, which enabled us to obtain theoretical cyclic voltammograms. Kinetic parameters such as diffusion coefficients, rate constants and transfer coefficients, describing the VO²⁺ ion reduction system, were estimated by fitting the theoretical curve with the experimental data. The parameters obtained were then evaluated on their extended applicability in various concentrations and scan rates. It was shown that the theoretical voltammograms obtained using the above parameters fitted well with the experimental curves for the scan rate variation from 2 to 20 V/sec, while the deviation increased in proportion to the VO²⁺ ion concentration.     

镍基芳烃加氢催化剂硫中毒的失活动力学

将某一时刻催化剂表面上活性中心数目与初始时刻活性中心数目之比定义为催化剂表观活性因子,并认为此活性因子包含在主催化反应速率系数的指前因子中。考虑活性中心在催化剂表面分布的不均匀性,在现有级数型失活动力学模型基础上,经推导得到表观活性因子的具体表达式及其极限式,该式在一般情况下为不可分。最后,结合之前报道的具有较高普适性的反应转化率方程式,得到催化反应转化率与运转时间的关系方程,并以Ni-B/SiO₂催化剂在噻吩存在下芳烃加氢反应为例加以验证。结果表明,所提出的失活动力学表达式可以较好地描述镍基催化剂硫中毒的行为,方程参量具有物理意义,方程可以较精确地拟合实验数据。