用化学平衡常数证明影响化学平衡的因素

在中学化学影响化学平衡条件的教学中,依据中学化学教材介绍的化学平衡常数表达式,来分析和证明影响化学平衡移动的因素,这是一种新教法。此教法能使学生快速明白和快速判断化学平衡移动的方向。同时,还能使学生进一步理解化学平衡常数的意义。     

Estimation of Ion-Exchange Equilibrium Constant Using Membrane Conductivity Data

Colloid Journal - The possibility of calculating the ionic composition of a membrane and the ion-exchange equilibrium constant on the basis of the concentration dependences of the specific...     

多重平衡标准平衡常数的计算方法及应用

介绍了多重平衡标准平衡常数的技巧性计算公式及适用范围,利用该公式解题简捷、快速、准确,还可以直观判断反应的方向性及反应程度。     

平衡常数的无热容近似式

本文基于自由能函数随温度变化极为缓慢的特性,按热力学基本关系式简捷地导得了一个不需热容数据的平衡常数近似式(简称无热容近似式),应用该式仅需一个温度下的K_p值和可自手册查得的标准生成热及标准熵的数据即可在较宽的温度范围内求得另一温度下的K_p值,且具有较高的准确度。     

Thermochemical Investigations of Tautomeric Equilibrium. Variation of the Calculated Equilibrium Constant with Binary Solvent Composition

Abstract

A conventional nonelectrolyte solution model which has led to successful predictive equations for solute solubility and infinite dilution chromatographic partition coefficients is extended to systems containing a tautomeric solute dissolved in a binary solvent mixture. The derived expression predicts that the tautomeric solute concentration in a binary solvent is a geometric average of the pure solvent ratios and permits calculation of solute-solvent association constants from variation of the stoichiometric tautomeric solute concentration ratios as a function of binary solvent composition. Experimental data for phenylazonaphthol dissolved in aqueous-ethanol and aqueous-acetone solvent mixtures is discussed in relation to the theoretical model.     

恒温恒容平衡体系中的反应物转化率随浓度变化规律的探讨

对恒温恒容条件下的可逆平衡体系在增大反应物浓度（即增大反应物的投料）后自身转化率的变化规律,进行了数学推导,得到了其转化率可能减小、不变或增大的结论。通过实例分析佐证了该结论的正确性,以避免在课堂教学和命题中出现错误。     

Phase Ratio and Equilibrium Constant in RP-HPLC Obtained from Octanol/Water Partition Constant Through Solvophobic Theory

The experimentally known dependence in RP-HPLC of the retention factor k′ on octanol/water partition coefficient (K _ow) has been examined based on solvophobic theory. The result showed that the dependence provides a means for the evaluation of phase ratio (Φ) of RP-HPLC columns, and of the equilibrium constant for a given compound and mobile phase. Using this theory, the phase ratio was evaluated for a set of seven different C18 columns (five having fully porous particles and two core–shell particles), and the equilibrium constants were calculated for four homologous series of compounds in two mobile phase systems. One mobile phase was methanol/aqueous solution of 0.1% H₃PO₄, and the other was acetonitrile/aqueous solution of 0.1% H₃PO₄. Besides providing the values for Φ for the evaluated columns, the results of the study indicated that for a specific composition of the mobile phase and for a given compound displaying only hydrophobic interactions, the equilibrium constant K(X) for different C-18 columns is basically the same. The data were further used to provide guidance in the selection of a chromatographic column for a specific separation based on K _ow values and chemical structure of the analytes. The study indicated that the separation of compounds with identical polar groups (or no polar groups) and with very close values for the K _ow cannot be achieved based only on hydrophobic interactions that dominate the separation on RP-type columns. Only column that displays polar interactions may provide a solution to such separations. For hydrocarbons with close K _ow values, the separation cannot be achieved even on columns with some polarity. On the other hand, even compounds with equal K _ow values, but with different functionalities can be separated on RP-HPLC columns without involving polar interactions. The compounds with different K _ow values are expected to be easily separated on RP-HPLC columns.     

运用溶度积计算平衡常数解答疑难问题

运用溶度积计算出与氢氧化镁沉淀相关的反应、与硫化铜沉淀相关的反应、与碳酸钙沉淀相关的反应的平衡常数。通过以上的计算与分析,让学生熟练掌握了运用溶度积计算化学平衡常数,从而判断反应能否发生。     

基于化学史和数据探究的“化学平衡常数”教学研究

分析了“化学平衡常数”的教材内容和相关教学设计,针对实际教学中存在的2个问题：简化的数据探究难以让学生体会到科学研究的复杂性;纯粹的知识性教学难以体现科学知识的价值和意义。提出在教学中融合化学史和数据探究,能帮助学生全面深入地理解概念,促进学生进一步认识科学本质和学科价值。     

Steady State and Equilibrium in Reversible Copolymerization at Constant Comonomer Concentrations

Selected aspects of copolymerization processes carried on at constant comonomer concentrations are analyzed theoretically and modeled by Monte Carlo method. It is confirmed that some combinations of initial parameters lead to stationary conditions of copolymer formation for both irreversible and reversible systems which can be regarded as the first‐order Markov chain process. However, this study shows that for many copolymerization systems the stationary conditions are attained only at high number‐average degree of polymerization DP _n, and for some reversible copolymerizations, attaining equilibrium, stationary conditions are not observed at all. The analysis shows that the chain length distribution (CLD) for copolymerization carried out under steady state conditions at constant comonomer concentrations, equal to equilibrium concentrations for infinitely high DP _n, is approximately described by the modified Bessel and exponential functions. This type of CLD is analytically proved and confirmed by the Monte Carlo simulations for the analogous homopolymerization process.     

Assessing the RAFT Equilibrium Constant via Model Systems: An EPR Study

Reversible addition‐fragmentation chain transfer (RAFT) equilibrium constants, K_eq, for the model system cyano‐iso‐propyl dithiobenzoate (CPDB) – cyano‐iso‐propyl radical (CIP) have been deduced via electron paramagnetic reso1494nce (EPR) spectroscopy. The CIP species is produced by thermal decomposition of azobis‐iso‐butyronitrile (AIBN). In solution of toluene at 70 °C, K_eq has been determined to be (9 ± 1) L · mol⁻¹. Measurement of K_eq = k_ad/k_β between 60 and 100 °C yields ΔE_a = (–28 ± 4) kJ · mol⁻¹ as the difference in the activation energies of k_ad and k_β. The data measured on the model system are indicative of fast fragmentation of the intermediate radical produced by addition of CIP to CPDB.

     

吲哚啉螺吡喃热致变色平衡常数的热测定法

报导了一种吲哚啉螺吡喃（SP）在丙酮溶液中热致变色平衡常数的新测定方法．通过分别检测紫外光照射SP后生成有色体的褪色过程和避光条件下其开环异构体与Cu（Ⅱ）的配合物形成过程，求得闭环无色体的开环速度常数kf和开环有色体的闭环褪色速度常数（kr）分别为4．94×10－4s－1和9．8×10－2s－1．利用Ke＝kf／kr，可求得Ke为5．0×10－3．此方法有助于解决Flannery等人方法中对不同溶剂ε估值所带来误差的问题．     

萘普生分子印迹拆分及亲和吸附平衡常数的测定

分子印迹 (Molecular imprinting)是一种新的、很有发展潜力的分离技术 [1～ 3 ] .该技术已成功地用于氨基酸、糖类及其衍生物和药物的手性分离 .萘普生是一种重要的非甾体消炎、解热和镇痛药 ,为了减少给药量和对人体产生的毒副作用 ,必须对其进行手性拆分 . Mosbach等 [4 ] 曾以 4-乙烯基吡啶为功能单体 ,利用分子印迹对外消旋萘普生进行了手性拆分 ,但 4-乙烯基吡啶使用前需经过减压蒸馏 ,使用不便 . Haginaka等 [5～ 7] 也采用 4-乙烯基吡啶为功能单体 ,以 (S) -萘普生为模板制得了均一粒径的分子印迹介质 .尽管分子印迹分离技术发展…     

胆红素—白蛋白复合物的化学平衡离解常数及结合自由能的测定

胆红素与血清白蛋白结合能形成一种水溶性的复合物［‘，’j，清除血液中过量的胆红素是人工肝辅助装置研究的热门课题［‘1．血液灌流所用材料必须具备与白蛋白竞争吸附胆红素的能力．而关于胆红素与白蛋白结合的平衡常数的测定尚未见报道．本文利用在不同白蛋白浓度和不同胆红素浓度的溶液中，CHP树脂对胆红素的吸附数据，求得胆红素一白蛋白复合物的化学平衡离解常数及结合自由能，方法简便易行．1实验部分1．1试剂及仪器壳聚糖（南开大学高分子所自制）；戊二醛（天津津宁精细化工厂），巳R．级；Span80（天津化学试剂三厂），C．P；…     

SOLO分类理论在高三化学平衡常数复习课教学中的应用

利用SOLO分类理论对高考试题进行能力结构分析,同时对学生在2021年全国甲、乙卷和湖北卷中的作答进行分析,诊断学生在化学反应原理主观题知识模块所处的SOLO水平。对比分析出大多数学生在解答化学反应原理试题的过程中处于多点结构水平,与高考试题呈现的SOLO水平有一定的差距。经访谈分析了不同SOLO水平的学生思维能力的不足之处,制定了高三渐进式复习策略。以化学平衡常数复习课为例,利用SOLO分类理论设计了多层级能力水平的复习内容和不同轮次复习的目标。     

平衡常数与正逆反应速率常数之间关系的探讨

从动力学与热力学的一致性原理出发,在知道可逆化学反应机理与不知道可逆化学反应机理的两种情况下,探讨了平衡常数与正逆反应速率常数之间的关系,确定了可逆反应平衡常数在不同情况下与正逆反应速率常数之间的关系式。     

基于氧化还原反应的配位平衡移动总反应平衡常数的推导

配位平衡的移动,可以遵从相同的“推导总反应的平衡常数”模式来做定性和定量的探讨。但在“氧化还原反应对配位平衡的影响”中,只是对化学反应做定性描述,总反应的平衡常数并没有推导,缺乏定量的探讨。原因在于氧化还原平衡常数与其他3大平衡常数不同,无法直接查得,需借助公式算出,具有隐蔽性,给总反应的推导造成了障碍。本文通过总反应平衡常数的推导解决了这个问题。     

凸显“定性与定量相结合”化学思想方法的教学设计——以“化学平衡常数”为例

将"定性与定量相结合"的思想方法运用于化学平衡常数的教学,利用经典实验和简单反应,以已有定性认知为基础,突出定量探究,彰显平衡常数定性和定量的双重特征,关注定性分析和定量分析的差异性和统一性,突出化学平衡常数的应用价值。     

Transient Incomplete Separation Facilitates Finding Accurate Equilibrium Dissociation Constant of Protein–Small Molecule Complex

Current practical methods for finding the equilibrium dissociation constant, K_d, of protein–small molecule complexes have inherent sources of inaccuracy. Introduced here is “accurate constant via transient incomplete separation” (ACTIS), which appears to be free of inherent sources of inaccuracy. Conceptually, a short plug of the pre‐equilibrated protein–small molecule mixture is pressure‐propagated in a capillary, causing fast transient incomplete separation of the complex from the unbound small molecule. A superposition of signals from these two components is measured near the capillary exit and used to calculate a fraction of unbound small molecule, which, in turn, is used to calculate K_d. Herein the validity of ACTIS is proven theoretically, its accuracy is verified by computer simulation, and its practical use is demonstrated. ACTIS has the potential to become a reference‐standard method for determining K_d values of protein–small molecule complexes.     

1981 Revisited

Ein unerwartet niedriger Etatzuwachs zwingt den britischen “Science and Engineering Research Council” zu drastischen Sparmaßnahmen. Betroffen sind vor allem Großprojekte in Physik und Astronomie sowie internationale Verpflichtungen. Die Gelder für Chemie werden halbiert.