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Thermodynamics in GeochemistryThe Equilibrium Model$
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Greg M. Anderson and David A. Crerar

Print publication date: 1993

Print ISBN-13: 9780195064643

Published to Oxford Scholarship Online: November 2020

DOI: 10.1093/oso/9780195064643.001.0001

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PRINTED FROM OXFORD SCHOLARSHIP ONLINE (oxford.universitypressscholarship.com). (c) Copyright Oxford University Press, 2021. All Rights Reserved. An individual user may print out a PDF of a single chapter of a monograph in OSO for personal use. date: 31 July 2021

Solid Solutions

Solid Solutions

(p.364) 15 Solid Solutions
Thermodynamics in Geochemistry

Greg M. Anderson

David A. Crerar

Oxford University Press

Real solutions of practical interest to Earth scientists do not behave ideally, although some do come fairly close. The problem of course lies in the stringent and unrealistic physical models we have prescribed for ideal solutions. The molecules of a gas do interact with each other, molecular forces within mixed component liquids really are non-uniform, and the different ions substituting for each other in solids are never exactly alike. So why bother defining an ideal solution in the first place if real systems do not behave that way? In fact, the ideal solution is a very useful artifice. It is something simple against which the behaviour of real solutions can be measured and compared. Our most fundamental definition of an ideal solution was With this as our reference, we can define a non-ideal solution as one for which the activity coefficient of each component i differs from unity The activity coefficient is the single quantity that expresses all deviations from non-ideality for each component of a solution. As we shall see, parameters other than the activity coefficient itself are frequently used to describe non-ideal behavior, but these could, if we wished, be related back to (15.1). Note that we say ⋎i, ≠1.0 in general; there are times when ⋎i = 1.0 for specific conditions (one set of T, P, Xi, etc.) even in highly non-ideal systems. This is just coincidental and certainly does not mean that the system is ideal at that particular point—the activity coefficient would have to be unity under all possible conditions for that to be the case.

Keywords:   applications, calculating solvi, excess functions, regular solutions, solvus, spinodal, virial equations

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