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The equation of phase equilibria in nano-sized crystal of metals has been established in terms of thermodynamic equilibrium. The thermodynamic parameters are calculated and the critical grain size for the stable high-temperature phase at room temperature is obtained. As an example, the critical grain size of β-Co at room temperature is determined at 35nm when the excess volume is 10%. The result agrees well with the experiment of Katakimi et al. The factors affecting the stability of β-Co are also discussed.