Solid-Solute Phase Equilibria in Aqueous Solution. XI. Aqueous Solubility and Standard Gibbs Energy of Cadmium Carbonate

The solubilities of CdCO₃ (otavite) in aqueous NaClO₄ solutions have been investigated as a function of ionic strength (0.15 I/mol-kg^–1 5.35, 25°C) and temperature (25°C T 75°C, I = 1.00 mol-kg^–1). A new Chemsage optimization routine was employed to simultaneously evaluate solubility data from this work and other sources, as well as standard electrode potentials determined at different ionic strengths. With the Pitzer equations the solubility constants, , were extrapolated to infinite dilution resulting in log and the ternary ion-interaction parameters ^S_Na,Cd = 0.19 and at 25°C. In addition, the following set of thermodynamic quantities can be derived from the present solubility data for otavite: _f G = –674.2±0.6 kJ-mol^–1; _f H = –755.3±3.4 kJ-mol^–1; S = 93±10 J-mol^–1K^–1. However, the present solubility data are also consistent with a recent determination of the standard entropy of otavite which leads to a recommended set of thermodynamic quantities [_f G (CdCO₃) = –674.2±0.6; _f H (CdCO₃) = –752.1±0.6; S (CdCO₃) = 103.9±0.2].     

Solid-Solute Phase Equilibria in Aqueous Solution. XII. Solubility and Thermal Decomposition of Smithsonite

The solubility constant of ZnCO₃, smithsonite, in aqueous NaClO₄ solutions hasbeen investigated as a function of temperature (288.15 T/K 338.15) atconstant ionic strength I = 1.00 mol-kg^–1. In addition, the solubility of zinccarbonate has been determined at 2.00 and 3.00 mol-kg^–1 NaClO₄ (298.15 K).The solubility measurements have been evaluated by applying the Daviesapproximation, the specific ion-interaction theory, and the Pitzer model, respectively.The thermodynamic interpretation leads to an internally consistent set ofthermodynamic data for ZnCO₃ (298.15 K): solubility constant log*K _p50 ⁰ = 7.25 ± 0.10,standard Gibbs energy of formation _i G (ZnCO₃) = (–777.3±0.6)kJ-mol^–1, standard enthalphy of formation _f H (ZnCO₃)= (–820.2±3.0) kJ-mol^–1,and standard entropy S (ZnCO₃) = (77±10)J-mol^–1 K.^–1. Furthermore, the DSCcurve for the thermal decarbonation of zinc carbonate has been recorded in orderto obtain the enthalpy of formation _fH (ZnCO₃) =(–820.2±2.0) from theheat of decomposition. Finally, our results are also consistent within theexperimental error limits with a recent determination of the standard entropy ofsmithsonite, leading to a recommended set of thermodynamic properties of ZnCO₃:      

一个普通化学实验:简易光伏电池的制作

本文介绍了一个简易光伏电池制作的教学实验。该实验包括两种光伏电池的制作,硫化铜/硅光伏电池和N719染料敏化的敏化光伏电池,适用于在大学一年级的普通化学实验课程中开设。文章对实验所包含的一系列基本化学原理进行了讨论,以方便该实验的进一步拓展,用于高年级的实验课程。     

Acid-Base Equilibria in Solutions of Polybasic Acids (Model and Experiment): I. Thermodynamic Dissociation Constants of Dibasic Acids

A procedure was developed for determining the thermodynamic dissociation constants of dibasic acids when the functional groups are neutralized jointly. The procedure is based on the electroneutrality and material balance laws. The equilibrium concentrations of all the ions and dibasic acid molecules are taken into account in calculation of the activity coefficients of the species formed in the course of neutralization and of the solution ionic strength.     

A Colorful Investigation of a Diprotic Acid: A General Chemistry Laboratory Exercise

A general chemistry laboratory experiment that can be completed in a single laboratory period is described that familiarizes students with the acid—base chemistry of a diprotic acid and with the use of visible spectroscopy to determine species concentrations. This experiment is a modified version of a previously described laboratory exercise developed for an upper-division quantitative analysis course. Students work in teams and as a class to generate different ionization states of various highly absorbing dyes. Both spectroscopic and potentiometric (pH) data is collected using LabWorks II stations, but other inexpensive pH meters and visible spectrometers (e.g., Spec 20s) are suitable. A spreadsheet template is used to determine the percent composition of various ionization states of a diprotic acid and to determine the pK_a values. Besides introducing students to fundamental tools and key chemical concepts, this laboratory is also inexpensive to operate and utilizes nontoxic, colorful solutions.     

几类醚化物的水溶性、碱水溶解性和酸解活性

本文对几类典型醚类化合物的水溶性、碱水(5%的Na₂SiO₃·9H₂O)溶解性和酸解活性进行了初步研究,查阅了这些醚类化合物的水溶性,并测定了其碱水溶解性、临界碱水不可溶醚当量以及在微量酸存在条件下的酸解活性,研究结果表明,对一般醚类化合物而言,当醚键中不含p-π共轭时其临界水不溶醚当量为116,临界碱水不溶醚当量为102;当醚键中含p-π共轭时其临界水不溶醚当量在56-100之间,临界碱水不溶醚当量在56-72之间,这些数据对光/热成像用活性醚化物阻溶/促溶剂的分子设计以及碱显影成像制版具有重大的指导意义。     

Chemical Reactions of Phosphonic Acids with Strong Bases in Aqueous Solutions. Volumetric Analusis

Common and individual regularities in changes of volumes in reactions of aqueous solutions of phosphonic acids [methanephosphonic, 1-aminoethanephosphonic, carboxymethahephosphonic, 1-hydroxyethane-1,1-diphosphonic, and nitriletris(methanephosphonic)] with aqueous solutions of sodium, tetramethyl-, and tetraethylammonium hydroxides at 298 K were revealed. The proposed explanation allows for the ionization of acids, the neutralization and hydration of ions, the presence of betaine forms, and the formation of proton chelates.     

Bridging the Gap Between First and Second Semester General Chemistry: A Laboratory Exercise

A simple yet challenging exercise that reviews many fundamental chemical concepts and laboratory techniques from first semester general chemistry is offered for use in the first laboratory period of the second semester general chemistry course. This exercise is easy to do and involves a minimal amount of equipment and reagents. Students at the authors school like this exercise because they get good results, yet feel challenged because they have to think for themselves.     

Protolytic Equilibria of Some N,N-Bis(2-carboxyethyl)aminoazobenzenesulfonic Acids in Aqueous Solution

4-[4-Bis(2-carboxyethyl)aminophenylazo]benzenesulfonic acid and 4-[2-bis(2-carboxyethyl)amino-4,5-dimethylphenylazo]benzenesulfonic acid were synthesized for the first time by azo coupling of diazosulfanilic acid with N,N-bis(2-carboxyethyl)aniline and N,N-bis(2-carboxyethyl)-3,4-xylidine, respectively. The acid ionization constants of the products were determined, their electron absorption spectra were measured, and schemes of acid-base equilibria in aqueous solution were proposed.     

A General Chemistry Experiment to Predict and Measure Functional-Group Stretching Frequencies

An experiment suitable for first-year students is reported. In this activity, students use a molecular modeling program to compute infrared spectra for a series of molecules. From the data obtained, students generate a group frequency chart and use it to identify unknowns. This provides students with an introduction to vibrational spectroscopy and the use of molecular modeling.     

Radiolysis of Aqueous Solutions of Benzoate Ion: A Radiation Chemistry Experiment for Undergraduates

This investigation describes the chemical effects of ionizing radiation on dilute aqueous solutions of benzoate ion. We have composed an experimental procedure that allows undergraduate chemistry students to identify and to quantitatively determine the amount of the products that are produced. The student investigators determine the absorbed dose that a sample receives when exposed to a ⁶⁰Co source, irradiate dilute aqueous solutions of benzoate ion, and analyze the resulting mixture of hydroxybenzoate ions using high-performance liquid chromatography. The radiolysis of dilute solutions of benzoate ion results in the formation of a mixture of ortho-, meta-, and para-hydroxybenzoate ions that are readily separated on a C₁₈ -Bondapak column. By the use of appropriate calibration curves, the yield (G values) of each of the isomers may be determined and compared.This paper was presented at the 15th Biennial Conference on Chemical Education, Waterloo, Ontario, Canada, August 1998 by N. Zevos and at the 26th Northeast Regional Meeting of the American Chemical Society by Evon Powell.     

“普通化学实验”英文课程的构建与实施

面向本校少年班学院大一学生开设了普通化学实验英文课程General Chemistry Laboratory。该课程涉及的知识面宽,突出实验的探究性;自编英文讲义,制作英文课件和教学网站;设计翻转课堂教学;实施多种对外交流模式,从听说读写各方面提高学生的英语水平,使学生的科学创新能力和英语应用能力均得到提高。     

无机及分析化学实验室管理的实践和探索

浙江大学无机及分析化学实验室在日常管理和教学辅助工作中开展了一系列的实践和探索,如开设循环实验、关注实验细节、加强安全教育与考核等。本文分析和总结了在实验室资源最优化、节约药品、保障仪器设备的运行、注重安全管理等方面所采取的一些行之有效的做法。     

Nickel Aqueous Speciation and Solubility at Ambient Conditions: A Thermodynamic Elegy

Summary.  This review reveals that, in contrast to the general opinion, the aqueous speciation of nickel is poorly known. Besides the fairly well established first hydrolysis constant, data are scarce and only poor estimates can be derived for higher Ni hydrolysis constants from a few solubility studies. The situation is even worse in the case of aqueous carbonate complexes. No reliable experimental study has been published so far and almost all numbers reported in thermodynamic databases are unacceptable estimates. In this review we scrutinise all these published estimates and propose expectation ranges of nickel carbonate complex stability through correlation with other known thermodynamic constants. Solubility constants for a few simple nickel solids are known or have been estimated from thermochemical data. However, none of these simple solids is of geochemical relevance at ambient conditions. Based on field evidence, classes of solids are identified which potentially govern nickel concentrations in ground and surface waters. Recent spectroscopic data indicate that magnesium clay minerals and layered double hydroxides are the most prominent candidates for nickel-bearing solids at ambient conditions. Corresponding author. E-mail: wolfgang.hummel@psi.ch Dedicated to the memory of Prof. Rolf Grauer Received January 14, 2003; accepted January 24, 2003 Published online May 15, 2003