Please go to the Copyright Clearance Center request page. In a third-party publication (excluding your thesis/dissertation for which permission is not required) If you want to reproduce the whole article If you are the author of this article, you do not need to request permission to reproduce figuresĪnd diagrams provided correct acknowledgement is given. Provided correct acknowledgement is given. If you are an author contributing to an RSC publication, you do not need to request permission To request permission to reproduce material from this article, please go to the Defining isochoric thermal capacity and isentropic compression at constant temperature and pressure, and introducing partial molar properties at constant temperature and molar volume, at constant molar entropy and pressure, and at constant molar entropy and molar volume The concept of a ‘partial fractional property’ is introduced to allow intensive properties of the system which are not independent variables to be treated in a similar fashion to the extensive ones.įinally, some observations concerning the thermodynamic meaning of a partial molar property are made. The origin of the non-Lewisian behaviour is ascribed to purely mathematical reasons. Their general relations to X B( T, p) are given and non-Lewisian properties are identified for each kind of partial molar properties. Generalized partial molar properties at constant temperature and molar volume X B( T, V m), at constant molar entropy and pressure X B( S m, p), and at constant molar entropy and molar volume X B( S m, V m) are introduced and briefly discussed.
A summary of thermodynamic relations among the usual X B( T, p) properties (those of the Lewisian type) is presented, and it is suggested that non-partial molar quantities be defined in order to fill the place of non-Lewisian partial molar properties in the thermodynamic formalism for Lewisian ones.
To express this behaviour, C V,B( T, p) and K S,B( T, p) are designated as non-Lewisian properties. Contrary to generally accepted views, their relations with C p,B( T, p) and with K T,B( T, p), respectively, which are rederived directly from the equations relating the parent extensive properties, are far from being similar to the relations involving the corresponding molar properties. This is shown to be true whenever the independent variables y and z, one thermal and the other mechanical, are intensive properties of the system.Ĭoncerning common partial molar properties, those defined at constant temperature and pressure, particular attention is paid to the partial molar isochoric thermal capacity C V,B( T, p) and to the partial molar isentropic compression K S,B( T, p). X being any thermodynamic extensive property of a homogeneous phase of fixed composition, it is proposed to consider X B( y, z) as a generalized partial molar property of substance B with respect to constant ( y, z) whenever X B( y, z)=( ∂ X/ ∂ n B) y, z, n′ where n′ indicates that all n are held constant apart from n B, complies with the condition. The concept and properties of partial molar quantities are presented and discussed in a generalized fashion within a thermodynamic framework.
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