搜索

x
中国物理学会期刊

熱力學中平衡與穩定之理論

CSTR: 32037.14.aps.7.132

THERMODYNAMICS OF EQUILIBRIUM AND STABILITY

CSTR: 32037.14.aps.7.132
PDF
导出引用
  • 本文首述如何應用一半滲透之壁使一物體所包含各種分子之數改變,因之决定此物體之熵與其各種分子數之關係,由此關係極易推出一物體在改變其形態時,如汽化凝結等,所應適合之平衡條件。且若形態不變,而發生內部化學作用時,其平衡條件亦易推得。次述如何由熵之增加原理推出能量最小之法則,然後應用此法則,輔以拉革蘭氏之不定乘子,以求得一物體之普遍平衡與穩定之條件。其穩定之條件且以各種不同之形式表示之。繼討論二元物體在平衡時之性質,隨之以多元物體之性質,求得一組方程式以决定當此物體之性質改變時,其温度壓力及各種分子之數如何改變。曾特別注意及溶液之性質,對於融點之降低與沸點之升高有一普遍之證明。最後推廣卜朗克氏關於並存形態之理論於多元物體,得與卜氏相似之結論。

     

    The dependence of the entropy of a homogeneous system on the composition is investigated with the help of a reversible adiabatic process which allows the change of composition by means of a semipermeable wall. The conditions of equilibrium for phase transition and for homogeneous chemical reaction are derived in a new way. Next the criterion of minimum energy for constant entropy and volume is derived from the principle of increase of entropy. This criterion is then applied to obtain the conditions of equilibrium and stability with the help of Lagrange's multipliers. The conditions of stability are expressed in several alternative forms. Next the equilibrium properties of a binary system are considered, and some types of phase diagram are explained by means of equations. The theory is extended to the general heterogeneous equilibrium of a system consisting of any number of independent components. A system of equations for the change of temperature, pressure, and composition are obtained and are solved by means of determinants. Next Planck's theory of a binary solution is extended to a solution consisting of several solute components, with the same conclusion regarding the lowering of freezing point as for a binary solation. Finally Planck's theory on the number of coexisting phases for a one-component system is extended to a system consisting of k components with the result that a state with σ coexisting phases is more stable than one with σ-1 phases, where σ is an integer not greater than k+2.

     

    目录

    /

    返回文章
    返回