Determination of chemical composition of solid inorganic substances and materials using the principles of stoichiography and voltammetry

The state of the art in determination of the phase composition of complex inorganic solids by chemical and electrochemical methods is discussed. The theoretical and practical essentials of stoichiography and the new stoichiographic method of differential dissolution (DD) are reported. The unique feature of this method is that reference samples of the analyzed solid phases are not necessary. The development of this stoichiographic method was strongly affected by voltammetry. The application of the DD method for determining the chemical composition of various substances and materials is presented. The complementary use of voltammetry and DD for the detection, identification, and quantitative determination of inhomogeneity of the chemical composition of high-temperature superconductors was shown to be efficient.     

Analytical Chemistry of Phases of Variable Composition and the Principles of Stoichiographic Determination of Such Phases in Multielement Multiphase Samples

The general problems of determining the stoichiometry and content of solid phases of variable composition in multielement multiphase substances are discussed. The possibilities and conditions of application of a reference-free stoichiographic method based on the differential dissolution (DD) of components for the analysis of samples containing spatially homogeneous and inhomogeneous phases are considered. The results of mathematical modeling of the DD process for a mixture of phases of constant and variable composition are presented. These data substantiate the use of the stoichiogram affinity criterion for the identification of spatially inhomogeneous phases of variable composition. Examples of applying the DD method to the phase analysis of various substances containing phases of variable composition are given.     

Calculations and interpretation of the results of stoichiographic analysis of solid multi-element multi-phase compounds and materials

Methods and approaches to the calculations and interpretation of the results of stoichiographic analysis of solid multi-element multi-phase compounds and materials using the flow mode of the differential dissolution (DD) method are reported. Special features of calculationls as well as the objective reasons for the necessity of obtaining more or less precise results of stoichiographic calculations are discussed. The details of the procedure of stoichiographic calculations, refinement, and interpretation of the results are considered on an example of the DD-analysis of the Co-Ni-Fe-Bi-K-P-Mo-O/SiO₂-catalyst for the selective oxidation and oxidative ammonolysis of hydrocarbons. The specific details and methods used for the estimation of the performance characteristics of the DD analytical procedure are discussed.     

Specific features of the dynamic mode of differential dissolution as of a method of phase analysis

The author considers the specific features of the separation properties of the stoichiographic method of differential dissolution (DD) and the role of thermodynamic and kinetic factors in the processes of the separation of solid mixtures. It is shown that the separation properties of DD should be characterized by selectivity and efficiency, as it is accepted in chromatography. The separation possibilities of DD are considered in characterizing uniformity, stoichiometry-nonstoichiometry of the elemental composition of phases, and also of their macro- and microstructures. The comparison of the principles and characteristics of DD, voltammetry, titrimetry, mass spectroscopy, and chromatography has led to the conclusion that the place of DD among the other methods is determined, primarily, by its unique property, namely, its standardless nature.     

Determination of the chemical composition of modified fiber glass silicate materials by differential dissolution

The paper presents the results of application of the stoichiographic method of differential dissolution (DD) to the analysis of modified aluminosilicate and zirconium silicate fiberglass materials (FGM) and related catalysts. Na-Al-Si and Na-Zr-Si FGM have been studied after sodium leaching-out and subsequent modification with Al, Co, and Pt additives. The conditions of detection, identification, and determination of different forms of FGM modifiers and the analysis of the surface of these samples are provided. The DD method has been used for the precise correction of the composition of the fiber glass sample surface.     

Stoichiographic Methods in the Analysis of Substances of Unknown Composition

A hierarchic structure of concepts of the chemical composition of substances, including substances of unknown composition, was proposed on the basis of physicochemical criteria. The latest achievements in the theory and practice of standardless stoichiographic methods for determining the molecular composition of substances (differentiating dissolution and ion chromatography) were considered.     

Stoichiographic determination of the composition and concentration of phases encapsulated in the bulk of a solid matrix phase

A two-step method of stoichiographic calculations used in the determination of the formulas of phases encapsulated in the bulk of matrices of another composition is proposed. At the first stage of calculations, the stoichiometric composition of the encapsulated phase is determined and, at the second step, the concentrations of this phase and the matrix are found. The use of this method in the analysis of oxide La–Cu catalysts by the method of differential dissolution ensures the detection of the phase La₁Cu₁ (La₂Cu₂O₅), incorporated within the matrix La₁Cu_0.5 (La₂CuO₄) phase.     

Stoichiography in the study of spatial heterogeneity of the chemical composition and structure of thin films and nanostructured systems

We present the principles of stoichiography and a reference-free stoichiographic differential (separating) dissolution method used to study the composition and structure of thin films and nanostructured systems: HTS films with 123 different compositions, Al–Au–Sn–Co–Mn, Si/SiO₂/Ni(Cr)–Cu–Cu2S, Cr–Cu–S, and Cu–S multilayer films, Bi–Ti–O films on Ru/SiO₂/Si, Mn_1–xZn _x S, and ZnS–EuS supports, and also nanostructured manganese ferrite in borate glass matrices, nanodisperse composite sorbents and the Co–Si–Pt–O/Al₂O₃ catalyst modified by Pt nanoparticles, and oxide catalyst precursor Fe₂Co/Al₂O₃ for the synthesis of carbon nanotubes.     

Determination of the chemical composition of supported vanadium-containing oxide catalysts by the differential dissolution method

The results of the application of the stoichiographic method of differential dissolution (DD) in the determination of the chemical composition of vanadium-containing catalysts are presented. In the studied catalyst series, amounts of vanadium were deposited onto TiO₂, SiO₂, Al₂O₃, ZrO₂, and Nb₂O₅. The catalysts were prepared by the impregnation method or by the spray drying method and thermally treated at different temperatures. The DD method was used for the precise correction of the phase composition of the V₂O₅/TiO₂ catalyst samples in order to determine the nature of the active component of these catalysts and obtain the correct information on their structure using the NMR method.     

Thermodynamic characteristics of ionic association in dimethylformamide solutions of barium iodide and zinc and lantane chlorides

Enthalpies of electrolyte transfer and differences between enthalpies of anions transfer from water to mixed solvent were defined on the basis of results from our own measurements of dissolution enthalpies of potassium acetate in mixed solvents acetonitrile-water and dimethylformamide-water of different composition, and of the literature data on dissolution enthalpies of other electrolytes in the same mixed solvents. These values are discussed with the aim of establishing the principles of solvatation for different anions in the studied mixed solvents.     

Stoichiography for investigation of the functional materials composition,structure, and properties

Principles of the stoichiography and differential dissolution method (DD) providing deep insight into the composition of mixtures containing unknown chemical compounds are considered. Compounds can be identified using their primary feature — the stoichiometry of elemental composition; reference samples of the compounds are not needed. The DD method makes it possible to analyze mixtures of crystalline and/or amorphous phases with constant and/or variable composition in the form of dispersed powders, ceramics, crystals, thin films and nanosize objects. Various aspects of the stoichiography and DD method application to investigation of composition, structure and properties of the functional materials are discussed.     

Mechanism of dissolution of sparingly soluble electrolytes

Recent constant composition dissolution studies of sparingly soluble calcium phosphates have revealed an interesting and unusual behavior in that the rates decreased, eventually resulting in effective suppression, even though the solutions remained undersaturated. Contrary to traditional theories of dissolution, these experimental results indicated the importance of not only the particle size on the dissolution rate but also the participation of critical phenomena. In these theories, it is assumed that when the dissolution reactions are initiated, they continue spontaneously until all solid phase has disappeared. In terms of these mechanisms, there are no critical phenomena in the dissolution mechanism. Although the crystal size decreases during dissolution, when the reaction is controlled by polypitting (formation and growth of pits), the edge free energy increases at the very first stage due to the creation of pits and dissolution steps. The constant composition experimental results demonstrate the development of surface roughness as the dissolution steps are formed, implying an increase of the total edge length during the reactions. In an exactly analogous mechanism to crystal growth, the participation of critical conditions involving dissolution steps is a possibility. In contrast to crystal growth, dissolution is a process of size reduction and, when the particle size is sufficiently reduced, critical phenomena become important so that the influence of size must be taken into consideration. This paper proposes such a model for dissolution reactions, and although these unusual phenomena probably apply to all mineral phases, they are more evident for sparingly soluble electrolytes in which the critical conditions are attained much more readily.     

Differential thermal analysis of some fibers containing chlorine

The differential thermal analysis curves of four fibers containing chlorine (Saran, Cordelan, Teklan and Kanekalon), and their blends, are influenced by experimental conditions, although not to the same extent as those of poly(vinyl chloride) resin in powder form. The curves were determined using two different (Du Pont) cells, and are discussed in terms of sample holder geometry and material composition. The importance of procedural variables in “fingerprint” applications of thermal analysis for routine fiber identification is re-emphasised.     

The electrochemistry of gold in acid aqueous solutions containing chloride ions

Results obtained with differently prepared gold electrodes in acid solutions containing chloride ion at temperatures ranging from 22 to 65°C are reported. Potentiostatic techniques and rotating disc electrodes were employed. The anodic dissolution, the onset of passivity and the cathodic deposition of the metal are investigated under different experimental conditions. The anodic dissolution of Au is discussed in terms of possible reaction mechanisms involving the participation of different adsorbed species. The onset of passivation is related to the depletion of chloride ion at the reaction interface. The experimental voltammograms can be reporduced by means of an equation which considers the diffusion of chloride ion, the activation polarization related to the dissolution of Au and the establishment of passivity.     

Oxidation of UO2(s) in aqueous solution

In this review the kinetics and mechanism of oxidative dissolution of UO₂(s), mainly under conditions of relevance for the safety assessment of a deep geological repository for spent nuclear fuel, are discussed. Rate constants for the elementary processes involved (oxidation of UO₂ and dissolution of oxidized UO₂) are used to calculate the rates of oxidative UO₂(s) dissolution under various conditions (type of oxidant, oxidant concentration and HCO₃ ⁻/CO₃ ²⁻ concentration) for which experimental data are also available. The calculated rates are compared to the corresponding experimental values under the assumption that the experimental numbers reflect the steady-state conditions of the system. The agreement between the calculated rates and the corresponding experimental ones is very good, in particular for the higher rates. In general, the calculated rates are somewhat higher than the experimental numbers. This can be due partly to the use of initial concentrations rather than steady-state concentrations in the calculations. The kinetic data are also used to quantitatively discuss the dynamics of spent nuclear fuel dissolution under deep geological repository conditions.      

Transpassive dissolution mechanism of ferrous alloys in phosphoric acid/acetic acid mixtures

The transpassive dissolution of Fe-12%Cr and Fe-25%Cr alloys in near-anhydrous phosphoric acid/acetic acid mixtures has been studied by conventional voltammetry and electrochemical impedance spectroscopy. Both steady-state and transient techniques point to two parallel pathways for the process involving oxidative dissolution of Cr as Cr(VI) and isovalent dissolution of Fe most probably mediated by an electrolyte-originating species. A simplified kinetic model of the process including only surface kinetic steps has been found to reproduce successfully both the steady-state and the small-amplitude AC response of the studied materials. The kinetic parameters of the model are determined and their relevance regarding the influence of the alloy and electrolyte composition on the relative importance of the two parallel pathways is discussed. The experimental data and model calculations indicate that the effect of acetic acid on the reaction steps related to dissolution of Fe is more significant.     

锈层下碳钢和耐候钢的微区和宏观腐蚀电化学行为

采用扫描电化学显微镜(SECM), 辅以极化曲线和电化学阻抗谱(EIS), 并结合SEM和XRD研究了耐候钢和碳钢在干湿交替环境下的腐蚀行为, 包括微区阳极溶解过程和阴极还原行为、 宏观腐蚀过程和微观结构及组成等. SECM测试结果表明, 锈层下碳钢和耐候钢的腐蚀过程都受阳极控制, 锈层的存在促进氧的还原. 宏观和微区电化学测试结果均表明, 在实验周期内, 初期形成的锈层降低了Fe阳极溶解速率, 从而提高碳钢和耐候钢的耐蚀性能, 后期形成的锈层由于其组成和结构特征的变化, 2种钢的腐蚀速率增加; 同时耐候钢的腐蚀速率较碳钢大, 且氧还原也较碳钢强, 有利于锈层的形成, 从而有利于长期的防护, 但是耐候钢的锈层在短期内并没有很好的保护性. 锈层不够致密, 呈疏松多孔状, 其组成主要有晶态的γ-FeOOH, Fe₃O₄和γ-Fe₂O₃等, 相同的干湿循环条件制备的耐候钢锈层较碳钢厚.     

Kinetics of corrosion and dissolution of uranium dioxide as a function of pH

A continuous flow-through reactor with a thin layer of solid particles (size ranging from 100 to 300 μm) was used to obtain a deeper knowledge on the mechanism of dissolution of UO₂ under oxidizing conditions. Using this methodology the dissolution rate of uranium dioxide was determined at three different oxygen partial pressures (5, 21, and 100% in nitrogen) and as a function of pH (between 3 and 12) in a noncomplexing medium. From the results of these experiments the following rate equation was derived: In addition, XPS characterizations were performed to determine the U(IV)/U(VI) ratio on the solid surface at different experimental times and conditions. These results showed that at acidic conditions (pH below 6.7) the final solid surface presents a stoichiometry close to UO₂, while at alkaline conditions the final solid surface average composition is close to UO_2.25. This information was integrated with the results of the leaching experiments to present a model for the mechanism of dissolution of uranium dioxide under the experimental conditions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 261–267, 1997.     

铝土矿有效铝含量测定影响因素研究

研究了影响铝土矿中有效铝含量测定的主要影响因素。主要探讨了样品粒度、均匀性对有效铝溶出效果的影响及样品组成对有效铝含量大小的影响。利用电感耦合等离子体原子发射光谱(ICP-AES)法测定铝土矿中有效铝含量、X射线荧光光谱(XRF)法测定铝土矿中总氧化铝含量和其它杂质成分含量,借助X射线衍射光谱(XRD)法对样品进行物相组成分析,确定各主要组成的结构和占比。将样品制备至0.106mm以下,均匀性好,精密度高,有效铝溶出率高。样品物相组成中三水铝石占比高,一水铝石占比低,与氢氧化钠低温条件更易反应,使溶出率高。通过加标回收实验验证方法的加标回收率为99.1%～101%,实验标准偏差为0.14%,相对标准偏差为0.003%,可对铝土矿有效铝的监控提供技术支撑。     

The Common Intermediates of Oxygen Evolution and Dissolution Reactions during Water Electrolysis on Iridium

Understanding the pathways of catalyst degradation during the oxygen evolution reaction is a cornerstone in the development of efficient and stable electrolyzers, since even for the most promising Ir based anodes the harsh reaction conditions are detrimental. The dissolution mechanism is complex and the correlation to the oxygen evolution reaction itself is still poorly understood. Here, by coupling a scanning flow cell with inductively coupled plasma and online electrochemical mass spectrometers, we monitor the oxygen evolution and degradation products of Ir and Ir oxides in situ. It is shown that at high anodic potentials several dissolution routes become possible, including formation of gaseous IrO₃. On the basis of experimental data, possible pathways are proposed for the oxygen‐evolution‐triggered dissolution of Ir and the role of common intermediates for these reactions is discussed.