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The parameters Phi and N of Miedema are quoted precise to the second decimalplace and are considered very accurate after adjustment in their values tocorrectly predict the signs of the heats of formation of more than 500 metallicbinary systems. In this paper, we argue that Phi is proportional to theelectronegativity (Chi) of metallic elements and that N^(1/3) is the valenceeffective on a linear bond. We show that, with the above hypothesis, Chi can bederived in the absolute sense, following Gordy, as the electrostatic potentialdue to the effective charge of the nucleus of an atom in a metal, felt at themid-point of a bond to the nearest atom. The exponent 1/3 has its origin in thehigh ligancy and resonance in metals. An excellent agreement with thehypothesis is observed for the hypoelectronic elements, while the buffer andhyperelectronic elements show interesting variations. It is argued that theunlike atom pair bond energies, which are correlated to the distribution ofbinary systems on the map constructed using the magnitudes of parameters delPhi and del N of Miedema, originate from the scatter in the distribution ofelements in the electronegativity versus N^(1/3)/R graph. Since it is thescatter that is important, we see that the small corrections effected byMiedema et al. to the parameters Phi and N are significant in deciding theenergies involved. An interpretation is provided for the energy effectsinvolved in the alloying of metals.

Energy effects on alloying through a re-interpretation of the parameters of Miedema