深入理解化学平衡常数及其应用——对2019年全国理综(Ⅰ卷)化学第28题的分析

在已有的化学平衡常数教学的基础上,提出认知化学平衡常数的新角度--化学平衡常数的多种表达式。依据教材中用浓度表示的化学平衡常数并结合理想气体状态方程,推导用物质的量分数及分压表示的化学平衡常数表达式,分析3者之间的区别和联系,进而应用化学平衡常数的多种表达形式解决2019年全国(Ⅰ卷)化学第28题中的相关问题,使学生深入理解解答这道高考试题的关键所在。同时,拓展了学生对平衡常数的认识,提升了学生灵活应用平衡常数解决问题的能力。     

基于认识模型建构与应用的化学教学设计*——“水溶液中的离子反应与离子平衡”一轮复习课

分析了“水溶液中的离子反应与离子平衡”主题内容,通过学生前测发现学生对这一部分内容的认识存在着认识水平较低、认识不够深入等问题。针对这一问题,在实际教学中通过构建水溶液中的离子反应与离子平衡认识模型的方式,创设真实的问题情境,引导学生明确任务类型、丰富认识角度、形成认识思路,从而使学生对主题内容的认识走向深入和系统。通过后测,分析了教学效果,进行了教学反思,为在教学实践中开展认识模型建构教学提供参考。     

Benchmark ab initio proton affinity and gas-phase basicity of α-alanine based on coupled-cluster theory and statistical mechanics

We determine the proton affinity (PA) and gas-phase basicity (GB) of amino acid α-alanine at a chemically accurate level by performing explicitly-correlated CCSD(T)-F12b/aug-cc-pVDZ geometry optimizations and normal mode vibrational frequency calculations as well as CCSD(T)-F12b/aug-cc-pVTZ energy computations at the possible neutral and protonated geometries. Temperature effects at 298.15 K considering translational, rotational, and vibrational enthalpy and entropy corrections are obtained via standard statistical mechanics utilizing the molecular geometries and the harmonic vibrational energy levels. Both the amino nitrogen (N) and the carbonyl oxygen (O) atoms are proven to be potential protonation sites and a systematic conformational search reveals 3 N- and 9 O-protonated conformers in the 0.00–7.88 and 25.43–30.43 kcal/mol energy ranges at 0 K, respectively. The final computed PA and GB values at (0)298.15 K in case of N-protonation are (214.47)216.80 and 207.07 kcal/mol, respectively, whereas the corresponding values for O-protonation are (189.04)190.63 and 182.31 kcal/mol. The results of the benchmark high-level coupled-cluster computations are utilized to assess the accuracy of several lower-level cost-effective methods such as MP2 and density functional theory with various functionals (SOGGA11-X, M06-2X, PBE0, B3LYP, M06, TPSS).     

基于曲线问题情境的信息化教学尝试*——以“沉淀溶解平衡”为例

基于高中生对实验曲线理解困难的现状,为挖掘实验曲线的教学价值,以沉淀溶解平衡为例,结合课堂演示实验和教学软件,设计了“宏观微观符号曲线”多重表征教学为一体的实验探究课。根据沉淀溶解平衡实验证据,绘制实验曲线,构建微观模型和图像,从而培养学生的证据收集与应用意识,提高学生对曲线的分析和理解能力,领会各种变化曲线的来源。在曲线理解的基础上建立“溶解平衡转化”思维模型,以此为开展“曲线融入式”的问题引导型实验教学提供参考案例。     

Thermodynamically equilibrium roton states of nanoparticles in molten and vapour phases

We show a possibility for a thermodynamically equilibrium nanocrystalline structure consisting of nanosized solid inclusions to appear in a melt just beyond the melting curve. Thermodynamic stability of the nanocrystalline structure in the melt results from the free energy lowering due to rotational motion of nanoparticles. The main contribution to the reduction of the free energy of the system is due to an increase in the rotational entropy and change in formation energy of nanocrystals, i.e. the nanocrystalline structure in the melt, like vacancies in a crystal, is an equilibrium defect structure of the melt. It is demonstrated that similar nanocrystalline structures can also appear in the vapour phase in the form of liquid nanodrops and in liquid solutions, e.g. in He II.     

Halide‐Free Diarylcalcium Complexes—Syntheses,Structures, and Stability

A general procedure was developed for the synthesis of diarylcalcium complexes by addition of KOtBu to arylcalcium iodides in THF. Intermediate arylcalcium tert‐butanolate dismutates immediately leading to insoluble tert‐butanolate precipitates of calcium. Depending on the steric demand and denticity of additional neutral aliphatic azabases, mononuclear or dinuclear complexes trans‐[Ca(α‐Naph)₂(thf)₄] ( 1 ), [Ca(β‐Naph)₂(thf)₄] ( 2 ), [Ca(Tol)₂(tmeda)]₂ ( 3 ), [Ca(Ph)₂(tmeda)]₂ ( 4 ), [Ca(Ph)₂(pmdta)(thf)] ( 5 ), [Ca(hmteta)(Ph)₂] ( 6 ), and [Ca([18]C‐6)(Ph)₂] ( 7 ) were isolated (Naph=naphthyl; meda=N,N,N′,N′‐tetramethylethylenediamine; pmdta= N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine; hmteta=N,N,N′,N′′,N′′′,N′′′‐hexamethyltriethylenetetramine). The Ca?C bond lengths vary between 250.8 and 263.5 pm, the ipso‐carbon atoms show low‐field‐shifted resonances in the ¹³C NMR spectra.     

Near-infrared spectroscopic measurements of volume expansion and composition of CO2-expanded ethyl acetate,acetone, tetrahydrofuran,acetonitrile, methanol-OD,and dimethyl sulfoxide

CO₂-expanded liquid (CXL) is a mixture of organic solvent with high-pressure CO₂ whose volume is increased by CO₂ dissolved in it. CXLs have attracted attention as tunable solvents, because the solvent properties can be widely controlled by the pressure. The volume expansion and the solubility of CO₂ were measured by near-infrared spectroscopy for 6 CXLs at various pressures up to 55 bar and 40 °C. The molarity of organic solvent was determined from the absorbance of the 3ν and 2ν + δ bands, and that of CO₂ was obtained from the area of the 3ν₃ band, whose peak shifted to higher frequency with increasing pressure due to a decrease in the molecular interaction around CO₂. The expansion coefficient was shown to be an increasing function of the pressure with larger slope at higher pressure, and the mole fraction of CO₂ in the liquid phase was an almost linearly increasing function of the pressure. The results were in quantitative agreement with the literature data measured by conventional sampling method, indicating the validity of the spectroscopic method.     

丙烯腈、己二腈和丙腈与水的二元体系液-液相平衡数据的测定和关联(英文)

采用平衡法测定了丙烯腈+水、己二腈+水、丙腈+水三个二元体系在不同温度(303.15、313.15、323.15、333.15K)下的液-液相平衡数据;并采用NRTL(α=0.2,α=0.3)模型和UNIQUAC模型对液-液平衡数据进行了关联.结果显示,NRTL和UNIQUAC模型对三个二元体系在不同温度下的互溶度关联的目标函数值均小于1×10-17,实验值与计算值吻合较好,绝对偏差小于0.009,关联精度较高.该研究结果可为丙烯腈、丙腈和水三元平衡溶解度数据的模拟和预测提供可靠的基础数据,并对电解二聚法生产己二腈中电解液的分离提纯工艺具有一定的指导意义.     

结合PBL的思维导图法在大学化学“四大平衡”教学中的应用

Taking the chemical equilibria including acid-base equilibrium, complexation equilibrium, precipitation equilibrium and redox equilibrium as an example, the application of the mind mapping combined with problem-based learning in university chemistry teaching is introduced.