Iron-Carbon Phase Diagram a Century ATV Ariance with Chemical Thermodynamics

"For about a century thermodynamically absurd facts have been propagated in conjunction with the iron-carbon phase diagram. These facts concern fundamental relationships of chemical thermodynamics. Attention is turned here to the discussion of only one of the relevant aspects of the subject, i.e. the definition of the thermodynamic activity of the solute and its implications for the iron-carbon solution.IntroductionThe view on the iron-carbon solution is characterized by the assumption that the solute may appear in two different forms, i.e. graphite and cementite. Accordingly, two carbon solubilities are differentiated, on the one hand for graphite and, on the other hand, for cementite. As a consequence, two versions of the phase diagram exist simultaneously, the application of which depends on the prevailing conditions, (i) the so-called stable phase diagram with graphite as solute and (ii) the metastable one that is based on the cementite-in-iron solution. These diagrams are joined together in the double phase diagram that originates from Heyn [l ], with the first ideas mainly going back to Stansfield [2] and Charpy [3].Thermodynamically, the most inadequate implication of the Fe-C double phase diagram is that the carbon activity may take values larger than unity. With the standard state of the activity being that of the pure substance, i.e. the Raoultian one, such a value implies the nonsensical existence ofa state purer than pure. The explanation of this physical state, ifthere is any, vaguely refers to supersaturation and, in the wider sense, to the physico-chemical phenomenon of metastability. Other aspects of chemical thermodynamics are likewise involved. Therefore, the comprehensive investigation into the present subject requires more topics to be considered than only one separate issue. Not only should the criticism of the present view be in the focus but also the discussion of new ideas capable of reconciling the experimental facts, known about the F e-C system, with the fundaments of chemical thermodynamics. All this, however, cannot be provided here because of the limited space available. As a consequence, in what follows only a part of the whole problem is under scrutiny, i.e. the definition of the thermodynamic activity and its role for the interpretation ofrelevant experimental facts."