Abstract
Isothermal and non-isothermal kinetics are classified according to the viewpoint of rational approach. The appropriate selection of basic quantities and constitutive equations is stressed. The extensive discussion recently focused to the meaning of the partial derivatives is reinvestigated and clarified considering the origin of following equation
whereα is the extent of reaction,T andt are the temperature and time respectively, andf represents a function. The meaning of partial derivatives is demonstrated in details. The disagreement sometimes claimed between the data evaluated by means of isothermal and non-isothermal kinetics is also reviewed, but no fundamental differences are established.
Résumé
Dans l'optique d'une approche rationnelle, on procède à un classement de la cinétique en régimes isotherme et non-isotherme. On met en évidence le choix judicieux de valeurs fondamentales et d'équations d'état. On étudie la discussion récente concernant la signification des dérivées partielles et l'on éclaircit la question en considérant l'équation
oùα est le degré d'avancement de la réaction,T ett la température et le temps,f une fonction. On discute les causes du désaccord quelquefois observé entre les données évaluées en régimes isotherme ou non-isotherme.
Zusammenfassung
Isotherme und nicht-isotherme Kinetik wurden entsprechend einer rationellen Annäherung klassifiziert. Die geeignete Auswahl der fundamentalen Mengen und konstitutiven Gleichungen wurde betont. Die neuerliche lebhafte Diskussion über die Bedeutung der partiellen Derivativen wurde überprüft und durch die Gleichung geklärt:
wobeiα den Reaktionsgrad,T undt die Temperatur und die Zeit,f eine Funktion bedeuten. Es wurde auch die in einigen Fällen beobachtete Nichtübereinstimmung der durch isotherme und nicht-isotherme Kinetik erhaltenen Daten behandelt.
РЕжУМЕ
с тОЧкИ жРЕНИь РАцИОН АльНОгО пОДхОДА клАссИФИцИРОВАНы Иж ОтЕРМИЧЕскАь И НЕИжОтЕРМИЧЕскАь кИ НЕтИкА. пОДЧЕРкНУтА НЕОБхОДИМОсть сОстВ ЕтстВУУЩЕгО ВыБОРА ОсНОВНых ВЕлИЧИН И пР ИМЕНьЕМых УРАВНЕНИИ. пРЕДМЕт шИРОкОИ ДИскУссИИ, НА пРАВльЕМОИ В пОслЕДНЕЕ ВРЕМь НА ж НАЧЕНИЕ ЧАстНых пРОИ жВОДНых, РАссМОтРЕН сНОВА И ДА Ны РАжЩьсНЕНИь ОтНОсИтЕльНО УРАВНЕ НИь
гДЕα — МЕРА РЕАкцИИ,T Иt — тЕМпЕРАтУРА И ВРЕ Мь, сООтВЕтстВЕННО, Иf — ФУНкцИь. РАссМОтРЕНО тОжЕ РАсхОжДЕНИЕ, ОБН АРУжИВАЕМОЕ ИНОгДА М ЕжДУ ДАННыМИ, РАссЧИтАННы МИ пОсРЕДстВОМ ИжОтЕРМ ИЧЕскОИ И НЕИжОтЕРМИ ЧЕскОИ кИНЕтИкИ.
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The authors are obliged to Dr. P. Holba of the Institute of Solid State Physics and Dr. P. Hrma of the Joint Laboratory for Silicate Research, The Czechoslovak Academy of Sciences, Prague, for their helpful suggestions and friendly discussions on this subject.
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Šesták, J., Kratochvíl, J. Rational approach to thermodynamic rrocesses and constitutive equations in isothermal and non-isothermal kinetics. Journal of Thermal Analysis 5, 193–201 (1973). https://doi.org/10.1007/BF01950368
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DOI: https://doi.org/10.1007/BF01950368