Cryoscopy of real solutions

Kawalec, B.

doi:10.1007/bf01904011

Cited by 4 publications

(4 citation statements)

References 13 publications

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“…It has also been noted [14,15,18,19 ] that lack of concentration equilibrium (and homogeneity) within the sample may contribute greatly to the discrepancies between observed and calculated values. The principal phenomena contributing to the lack of concentration equilibrium are deviations from ideality in the liquid phase and solubility of minor components in the solid major component.…”

mentioning

confidence: 93%

“…The practical solution that has been used to bring theory and experiment into closer agreement is a redefinition of the state of equilibrium (the solid of the two phase systems containing the lesser component in veins or pockets) and stimulating experimentally the investigated system to conform with this state of quasi-equilibrium by quenching. This has been more or less explicitly expressed in several publications [14,15,18,19].…”

mentioning

confidence: 93%

“…The discussion of assumptions upon which derivation of Equations 1-4 has been based is given elsewhere [15]. The assumptions of idea/liquid solution and zero solid solution are essential to the development of the relationships.…”

mentioning

confidence: 99%

“…In order to extract all the information contained in this relation and particularly the total amount of impurities within the investigated system, various theories have been proposed [12,15], each assuming an ideal system. The results of those theories have been summarized in Equations 1 -4.…”

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confidence: 99%

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Dynamic purity determinations. I. Location of the solidus by nuclear magnetic resonance

Kawalec

Houser

Garn

1982

Journal of Thermal Analysis

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The error in purity determinations by differential scanning calorimetry has been studied on two different kinds of systems, metallic and organic, the latter with different types of impurities added. The organic systems have been corrected for solid-solubility error by a nuclear magnetic resonance technique.The impurities chosen for the organic systems were either quite dissimilar to the matrix or similar enough to render solid solution probable. This solid solution leads to deviations from the equation used for dynamic purity determinations. The nuclear magnetic resonance determination of the solidus establishes the proper starting temperature for area summation on a DSC curve.Thermoanalytical techniques are so generally useful that it is not at all difficult to establish new applications or deduce relationships on the basis of some experimental data-then find that there is substantial limitation on that application or concept. This senior author (PDG) has sought, from time to time, to examine some concepts that have developed in thermal analysis or are testable by thermal analysis to prove or disprove [1][2][3][4][5][6][7][8] or to delineate their limits [9, 10, this work].This program of research was undertaken to evaluate the potential error inherent in the purity determination methods which depend upon the assumption of ideal liquid solution but zero solid solution. Impurities are highly probable in real systems and in any real system the most probable impurities are materials closely related in chemical structure to the matrix material because of their origin or processing.The well known effect of small amounts of impurities on melting behavior of crystalline compounds, i.e., lowering of their melting points, provides an excellent basis for purity determinations by various methods (time dependent and time independent). There are three main advantages of these methods: first, simplicity and speed of some of them, viz. the time dependent ones; second, sensitivity which is of such magnitude that it can be compared with the best methods known, for instance, high temperature mass spectrometric analysis [10]; third, a firm base upon thermodynamic principles which means that no reference materials need to be applied. Experimentally, in purity determinations based on lowering the melting point

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confidence: 93%

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confidence: 93%

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confidence: 99%

mentioning

confidence: 99%

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Dynamic purity determinations. I. Location of the solidus by nuclear magnetic resonance

Kawalec

Houser

Garn

1982

Journal of Thermal Analysis

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Ternary System C-Fe-Ti

2012

Ternary Steel Systems: Phase Diagrams and Phase Transition Data

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Calorimetric test of purity I

Kiss

Seybold

Meisel

1981

Journal of Thermal Analysis

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Relationships of various levels for the thermodynamical description of two-component eutectic systems have been investigated. It has been established that the van't Hoff relationship describes the melting curve dH vs. T with satisfactory accuracy, but for its practical application a modification of the mathematical character, maintaining the physical content of the equation, is needed. The interpretation and the mode of application of the modified equation are given.

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Cryoscopy of real solutions

Cited by 4 publications

References 13 publications

Dynamic purity determinations. I. Location of the solidus by nuclear magnetic resonance

Dynamic purity determinations. I. Location of the solidus by nuclear magnetic resonance

Ternary System C-Fe-Ti

Calorimetric test of purity I

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