Concerning the problem of the isokinetic relationship. I. A statistical mechanical model

1983 ◽  
Vol 36 (10) ◽  
pp. 1903 ◽  
Author(s):  
W Linert ◽  
AB Kudrjawtsev ◽  
R Schmid
Keyword(s):  
Frequency Factor ◽  
Isokinetic Temperature ◽  
Reaction Series ◽  
Empirical Coefficient ◽  
Isokinetic Relationship ◽  
Exponential Factor ◽  
Statistical Mechanical Model ◽  
Statistical Mechanical ◽  
The Common

The equation for the rate constant derived from the statistical theory of kinetics is compared with the common Arrhenius equation. Thereby the pre-exponential factor and the activation energy can be expressed by means of the theoretical quantities, frequency factor (Z0), oscillator number (s), and potential barrier height (E). In these terms the isokinetic relationship can be represented by the equation (c- c) = b(E-E) where c is s- 1 and the bars denote the means in the reaction series under consideration. The empirical coefficient b, in connection with the numerical value of the isokinetic temperature, is proposed to be used as a criterion for the classification of reaction series. The model is exemplified by means of an organic SN2 reaction.

Concerning the Problem of the Isokinetic Relationship. IV. The Evaluation of the Isosubstituent Hammett Parameter by Means of Isokinetic and Isoequilibrium Temperatures

1986 ◽  
Vol 39 (2) ◽  
pp. 199 ◽  
Author(s):  
W Linert
Keyword(s):  
Temperature Dependence ◽  
Activation Parameters ◽  
Common Point ◽  
Isokinetic Temperature ◽  
Benzoic Acids ◽  
Reaction Series ◽  
Isokinetic Relationship ◽  
The Common ◽  
Point Of Intersection ◽  
Hammett Parameter

The interrelation between the isosubstituent and the isokinetic relationship is developed and tested for several Hammett reaction series. Two methods of approach to relate the temperature dependence of Arrhenius and Hammett plots are given, one utilizing the isoequilibrium temperature of the ionization of benzoic acids and the other the isokinetic temperature of the respective Hammett reaction series. The efficiency of the approaches for the evaluation of the coordinates of the common point of intersection in the Hammett plot, i.e. the characteristics of the isosubstituent relationship, are compared with each other and with experimental results. With the former approach, by using the activation parameters of only one (commonly the unsubstituted ) member of the series, the temperature dependence of a Hammett line can be predicted provided that the isokinetic temperature of the Hammett series does not approach the experimental temperature range. Otherwise the latter approach must be used which, however, needs the temperature dependence of at least two (or better more) members of the reaction series.

Concerning the problem of the isokinetic relationship. II. The physical significance of the degrees of freedom in the statistical-mechanical model

1984 ◽  
Vol 37 (6) ◽  
pp. 1139 ◽  
Author(s):  
W Linert ◽  
AB Kudrjawtsev
Keyword(s):  
Degrees Of Freedom ◽  
Potential Barrier Height ◽  
Physical Significance ◽  
Reaction Series ◽  
Isokinetic Relationship ◽  
Fitting Procedure ◽  
Statistical Mechanical Model ◽  
Complete Form ◽  
Statistical Mechanical ◽  
The Relationship

The statistical model presented recently for the isokinetic relationship is developed. The physical meaning of the degrees of freedom (s) is explained in terms of ∆Cp‡, i.e. the change in the specific heat between ground and activated states: ∆Cp‡ =-(s-1)R In the case where (s-1)/(E/kBT) cannot be neglected the relationship is ∆Cp‡=-(s-1)(1-kBT/E)R where E denotes the potential barrier height. The results from a digital fitting procedure for the complete form of the model are compared with those obtained from the simplified equations for 'energy-barrier-controlled' reaction series.

Concerning the Problem of the Isokinetic Relationship. III. The Temperature-Dependance of the hammett Equation

1985 ◽  
Vol 38 (5) ◽  
pp. 677 ◽  
Author(s):  
W Linert ◽  
R Schmid ◽  
AB Kudrjawtsev
Keyword(s):  
Benzoic Acid ◽  
Hammett Equation ◽  
Reaction Series ◽  
Temperature Dependent ◽  
Isokinetic Relationship ◽  
A Value ◽  
The Common ◽  
Point Of Intersection ◽  
Temperature Dependance ◽  
The Relationship

It is shown that the temperature-dependence of the Hammett equation is, in contrast to tradition, both physically and experimentally better described by means of temperature-dependent σ and temperature- independent ρ (termed ρo). The relationship between ρo and the customary (temperature dependent) ρ is ρT = ρo(1/T-1/Tbiso)/(1/T-1/Tbiso) where Tbiso , is the isoequilibrium temperature of the benzoic acid ionization, for which the present analysis suggests a value of -255 K, and T is 298 K. In these terms, the temperature variation of the Hammett equation can be evaluated by supplying merely E(u)a (the activation energy for the reaction of the unsubstituted reactant) and ρo, in that the σ value for the isokinetic substituent , i.e., the abscissa of the common point of intersection in the Hammett plot, is σiso = (1/T-1/Tbiso)E(u)a/(2.303Rρo) = E(u)a/(2630po) Further, ρo I related to energies ρo = E(u)a/(ΔH°u-ΔH°s(iso))where ΔH°u and ΔH°s(iso) are the ionization enthalpies of the parent benzoic acid and that bearing the isokinetic substituent , respectively. Analogous equations apply to thermodynamic reaction series when substituting E(u)a for ΔH°u(series). Along these lines the interpretation of the customary Hammett plot is advanced.

Philosophcal review of h. white̕s tropological theory in the context of the new philosophy of history

2020 ◽  
Vol 3 (152) ◽  
pp. 92-99
Author(s):  
S. M. Geiko ◽  
◽  
O. D. Lauta
Keyword(s):  
Modern Science ◽  
Historical Knowledge ◽  
Text Organization ◽  
The Social ◽  
History Of ◽  
Actual Material ◽  
The Common ◽  
Historical Nature ◽  
Selection Of

The article provides a philosophical analysis of the tropological theory of the history of H. White. The researcher claims that history is a specific kind of literature, and the historical works is the connection of a certain set of research and narrative operations. The first type of operation answers the question of why the event happened this way and not the other. The second operation is the social description, the narrative of events, the intellectual act of organizing the actual material. According to H. White, this is where the set of ideas and preferences of the researcher begin to work, mainly of a literary and historical nature. Explanations are the main mechanism that becomes the common thread of the narrative. The are implemented through using plot (romantic, satire, comic and tragic) and trope systems – the main stylistic forms of text organization (metaphor, metonymy, synecdoche, irony). The latter decisively influenced for result of the work historians. Historiographical style follows the tropological model, the selection of which is determined by the historian’s individual language practice. When the choice is made, the imagination is ready to create a narrative. Therefore, the historical understanding, according to H. White, can only be tropological. H. White proposes a new methodology for historical research. During the discourse, adequate speech is created to analyze historical phenomena, which the philosopher defines as prefigurative tropological movement. This is how history is revealed through the art of anthropology. Thus, H. White’s tropical history theory offers modern science f meaningful and metatheoretically significant. The structure of concepts on which the classification of historiographical styles can be based and the predictive function of philosophy regarding historical knowledge can be refined.

scholarly journals Exercise Addiction and Perfectionism: A Systematic Review of the Literature

2021 ◽  
Vol 8 (1) ◽  
pp. 144-155 ◽  
Author(s):  
Gizem Çakın ◽  
Ignatius Darma Juwono ◽  
Marc N. Potenza ◽  
Attila Szabo
Keyword(s):  
International Classification Of Diseases ◽  
Situational Factors ◽  
Future Research ◽  
Statistical Manual ◽  
Exercise Addiction ◽  
Diagnostic And Statistical Manual ◽  
Classification Of Diseases ◽  
The Common ◽  
The Relationship

Abstract Background and aims Exercise addiction may be conceptualized as a behavioral addiction in which a person develops an unhealthy obsession with exercise and physical activity. While exercise addiction is not a formally recognized disorder in the Diagnostic and Statistical Manual or the International Classification of Diseases, it has been studied and connected to both personal and situational factors. Perfectionism is a feature that has been strongly linked to exercise addiction. The objective of this systematic literature review, performed by following the PRISMA protocol, was to examine relationships between exercise addiction and perfectionism while also considering the subdimensions of perfectionism in different groups. Methods Three databases (PsycINFO, PubMed/Medline, and SPORTDiscus) were examined. Sixty relevant articles were identified, of which 22 met inclusion criteria. Results The findings substantiate that perfectionism and its dimensions are weakly or moderately related to exercise addiction. This relationship has been observed in adults, adolescents, athletes, and patients with eating disorders. Of the 22 studies examined, only one did not identify an association between perfectionism or its subdomain(s) and exercise addiction. However, in most studies, the common variance between perfectionism and exercise addiction is relatively small, raising questions regarding the clinical relevance of the relationship. Conclusion Perfectionism is related to exercise addiction, but the strength of the relationship varies in different circumstances, which should be examined in future research.

Classifying precontractual liability: a comparative analysis

Legal Studies ◽  
2001 ◽  
Vol 21 (2) ◽  
pp. 153-191 ◽  
Author(s):  
Joachim Dietrich
Keyword(s):  
Common Law ◽  
Civil Law ◽  
Tort Law ◽  
Contract Law ◽  
Common Elements ◽  
Ongoing Debate ◽  
Unjust Enrichment ◽  
The Common ◽  
Initial Focus

The common law has solved questions of liability arising in the context of precontractual negotiations by resort to a range of different doctrines and approaches, adopting in effect ‘piecemeal’ solutions to questions of precontractual liability. Consequently, debate has arisen as to how best to classify or categorise claims for precontractual work and as to which doctrines are best suited to solving problems arising from anticipated contracts. The purpose of this article is to consider this question of how best to classify (cases of) precontractual liability. The initial focus will be on the ongoing debate as to whether principles of contract law or principles of unjust enrichment can better solve problems of precontractual liability. I will be suggesting that unjust enrichment theory offers little by way of explanation of cases of precontractual liability and, indeed, draws on principles of contract law in determining questions of liability for precontractual services rendered, though it does so by formulating those principles under different guises. Irrespective, however, of the doctrines utilised by the common law to impose liability, it is possible to identify a number of common elements unifying all cases of precontractual liability. In identifying such common elements of liability, it is necessary to draw on principles of both contract and tort law. How, then, should cases of precontractual liability best be classified? A consideration of the issue of classification of precontractual liability from a perspective of German civil law will demonstrate that a better understanding of cases of precontractual liability will be gained by classifying such cases as lying between the existing categories of contract and tort.

The OMT Classification of Congenital Anomalies of the Hand and Upper Limb

Hand Surgery ◽  
2015 ◽  
Vol 20 (03) ◽  
pp. 336-342 ◽  
Author(s):  
Michael A. Tonkin ◽  
Kerby C. Oberg
Keyword(s):  
Upper Limb ◽  
Congenital Anomalies ◽  
Limb Development ◽  
Main Group ◽  
International Federation ◽  
Scientific Committee ◽  
Current Status ◽  
Thumb Duplication ◽  
The Common

The Oberg, Manske and Tonkin (OMT) Classification of congenital anomalies of the hand and upper limb uses dysmorphological terminology, placing conditions in one of three groups: Malformations, Deformations and Dysplasias. The main group, Malformations, is further subdivided according to whether the whole of the limb is affected or the hand plate alone, and whether the primary insult involves one of the three axes of limb development and patterning or is non-axial. The common surgical diagnoses, such as thumb duplication and thumb hypoplasia, are then placed within this framework. Recently the International Federation of Societies for Surgery of the Hand Scientific Committee for Congenital Conditions approved the OMT Classification as a timely and appropriate replacement of the previously accepted Swanson Classification. This review charts the development of and modifications to the OMT Classification and its current status.

Statistical-mechanical model of protein precipitation by nonionic polymer

AIChE Journal ◽  
1990 ◽  
Vol 36 (10) ◽  
pp. 1517-1528 ◽  
Author(s):  
Hari Mahadevan ◽  
Carol K. Hall
Keyword(s):  
Mechanical Model ◽  
Protein Precipitation ◽  
Nonionic Polymer ◽  
Statistical Mechanical Model ◽  
Statistical Mechanical
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