High Temperature Mass Spectrometric Study of Thermodynamic Properties and Vaporization Processes of Oxide Systems: Experiment and Modeling

Stolyarova, V. L.

doi:10.2174/1874396x01307010057

Cited by 7 publications

(6 citation statements)

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“…Th is paper is the continuation of the systematic studies of ternary silicate glass-forming melts obtained by Knudsen eff usion mass spectrometric method that are summarized in the following reviews [1][2][3][4][5][6][7]. It was shown that the main regularities of the vaporization of oxide systems were in agreement with the acid-based concept of interactions in the oxide melts.…”

Section: Introductionmentioning

confidence: 91%

Vaporization and thermodynamics of glasses and glass-forming melts in ternary oxide systems

Stolyarova¹

2017

ASSC

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Innovation development of the approaches for preparation and application of advanced materials requires the knowledge on vaporization processes and thermodynamic properties of glass-forming oxide systems. Th ese data obtained by high temperature mass spectrometric method in the IntroductionAs well known design of the advanced glass materials requires the reliable information on vaporization processes and thermodynamic properties of glass-forming melts. Th is paper is the continuation of the systematic studies of ternary silicate glass-forming melts obtained by Knudsen eff usion mass spectrometric method that are summarized in the following reviews [1][2][3][4][5][6][7]. It was shown that the main regularities of the vaporization of oxide systems were in agreement with the acid-based concept of interactions in the oxide melts. It was also repeatedly illustrated that the data on determination of thermodynamic functions in oxide systems were satisfi ed the main requirements for the confi rmation of their reliability in comparison with the results obtained by the electromotive force method and the high temperature solution calorimetric method. In the current study the high-temperature behavior of the following ternary glass-forming melts will be considered based on the PbO-B 2 O 3 -SiO 2 , CdO-B 2 O 3 -SiO 2 , ZnO-B 2 O 3 -SiO 2 , Bi 2 O 3 -B 2 O 3 -SiO 2 and Bi 2 O 3 -GeO 2 -SiO 2 systems. Th e subjects of this consideration have the wide range of practical applications in the production of glasses, enamels, glazers and ceramics as well as in the various high temperature technologies such as obtaining of optical fi bers and others. Since 1959 when Knudsen eff usion mass spectrometric method was suggested to study the vaporization processes and thermodynamic properties of inorganic compounds [8] till nowadays this approach still one of the powerful tool of high temperature chemistry of inorganic materials including multicomponent glass-forming

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Section: Introductionmentioning

confidence: 91%

Vaporization and thermodynamics of glasses and glass-forming melts in ternary oxide systems

Stolyarova¹

2017

ASSC

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“…Bencze and colleagues [234][235][236] have determined binary and ternary interaction parameters from KEMS data for a number of alloys. Stolyarova and colleagues 5,189,[193][194][195][196]200,201 have determined interaction parameters for a number of oxide systems using KEMS data.…”

Section: Solution Models and Model Parameters From Kemsmentioning

confidence: 99%

“…Following the publication of the monograph by Stolyarova and Semenov, 5 a number of reviews dealing with the vaporization and thermodynamic properties of oxide systems studied using KEMS at high temperatures have been completed 185–202 . The general overview in this area was presented in the series of publications from decade to decade 185–190 .…”

Section: Measurements Of Partial Pressures and Thermodynamic Properti...mentioning

confidence: 99%

“…Semenov, 5 a number of reviews dealing with the vaporization and thermodynamic properties of oxide systems studied using KEMS at high temperatures have been completed. [185][186][187][188][189][190][191][192][193][194][195][196][197][198][199][200][201][202] The general overview in this area was presented in the series of publications from decade to decade. [185][186][187][188][189][190] We can delineate them into three main groups: glassforming oxide systems, [191][192][193][194][195][196] ultrahigh-refractory oxide systems mainly based on 2, [197][198][199] modeling approaches developed using the Knudsen effusion mass spectrometric thermodynamic data on oxide systems for the prediction of their high-temperature behavior, 189,[193][194][195][196]200,201 and comparison to thermodynamic data that may be obtained at high temperatures using KEMS and differential thermal analysis.…”

Section: Following the Publication Of The Monograph By Stolyarova Andmentioning

confidence: 99%

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Knudsen effusion mass spectrometry: Current and future approaches

Jacobson,

Colle,

Stolyarova

et al. 2024

Rapid Comm Mass Spectrometry

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RationaleKnudsen effusion mass spectrometry (KEMS) has been a powerful tool in physical chemistry since 1954. There are many excellent reviews of the basic principles of KEMS in the literature. In this review, we focus on the current status and potential growth areas for this instrumental technique.MethodsWe discuss (1) instrumentation, (2) measurement techniques, and (3) selected novel applications of the technique. Improved heating methods and temperature measurement allow for better control of the Knudsen cell effusive source. Accurate computer models of the effusive beam and its introduction to the ionizer allow optimization of such parameters as sensitivity and removal of background signals. Computer models of the ionizer allow for optimized sensitivity and resolution. Additionally, data acquisition systems specifically tailored to a KEMS system permit improved quantity and quality of data.ResultsKEMS is traditionally utilized for thermodynamic measurements of pure compounds and solutions. These measurements can now be strengthened using first principles and model‐based computational thermochemistry. First principles can be used to calculate accurate Gibbs energy functions (gefs) for improving third law calculations. Calculated enthalpies of formation and dissociation energies from ab initio methods can be compared to those measured using KEMS. For model‐based thermochemistry, solution parameters can be derived from measured thermochemical data on metallic and nonmetallic solutions. Beyond thermodynamic measurements, KEMS has been used for many specific applications. We select examples for discussion: measurements of phase changes, measurement/control of low‐oxygen potential systems, thermochemistry of ultrahigh‐temperature ceramics, geological applications, nuclear applications, applications to organic and organometallic compounds, and thermochemistry of functional room temperature materials, such as lithium ion batteries.ConclusionsWe present an overview of the current status of KEMS and discuss ideas for improving KEMS instrumentation and measurements. We discuss selected KEMS studies to illustrate future directions of KEMS.

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“…Acid-base theories (see below) incorporate both thermodynamic and molecular constraints. Acid-base concepts have been applied fruitfully in oxide systems in the solid, molten, and glassy states, as well as in vaporization processes [2][3][4][5][6][7][8]. It is common…”

Section: Introductionmentioning

confidence: 99%

Acid–Base Properties of Oxides Derived from Oxide Melt Solution Calorimetry

Navrotsky

Корытцева

2023

Molecules

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The paper analyzes the relationships among acid–base interactions in various oxide systems and their thermodynamics. Extensive data on enthalpies of solution of binary oxides in oxide melts of several compositions, obtained by high-temperature oxide melt solution calorimetry at 700 and 800 °C, are systematized and analyzed. Oxides with low electronegativity, namely the alkali and alkaline earth oxides, which are strong oxide ion donors, show enthalpies of solution that have negative values greater than −100 kJ per mole of oxide ion. Their enthalpies of solution become more negative with decreasing electronegativity in the order Li, Na, K and Mg, Ca, Sr, Ba in both of the commonly used molten oxide calorimetric solvents: sodium molybdate and lead borate. Oxides with high electronegativity, including P2O5, SiO2, GeO2, and other acidic oxides, dissolve more exothermically in the less acidic solvent (lead borate). The remaining oxides, with intermediate electronegativity (amphoteric oxides) have enthalpies of solution of between +50 and −100 kJ/mol, with many close to zero. More limited data for the enthalpies of solution of oxides in multicomponent aluminosilicate melts at higher temperature are also discussed. Overall, the ionic model combined with the Lux–Flood description of acid–base reactions provide a consistent and useful interpretation of the data and their application for understanding the thermodynamic stability of ternary oxide systems in solid and liquid states.

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High Temperature Mass Spectrometric Study of Thermodynamic Properties and Vaporization Processes of Oxide Systems: Experiment and Modeling

Cited by 7 publications

References 50 publications

Vaporization and thermodynamics of glasses and glass-forming melts in ternary oxide systems

Vaporization and thermodynamics of glasses and glass-forming melts in ternary oxide systems

Knudsen effusion mass spectrometry: Current and future approaches

Acid–Base Properties of Oxides Derived from Oxide Melt Solution Calorimetry

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