On the Formation of Physical Chemistry in the later 19th Century

物理化学形成过程中的主要部分是化学热力学的建立，化学热力学的建立与化学动力学密切相关。非均相平衡理论和离解平衡理论被认为是化学热力学形成的基本力矩。1858年，G·基尔霍夫第一个将热力学原理应用于解题。他的理论对A.Horstmann、C.M.Guldberg、H.von Helmholtz等人的研究有很大帮助。2.正是解离平衡理论奠定了化学热力学形成的初级阶段。1873年，霍斯特曼被认为是第一个将热力学第二定律应用于化学过程的化学家，他在有关离解平衡的理论上达到了定性的高水平，建立在熵最大化原理的基础上。霍斯特曼对化学过程与热力学定律的内在联系、微观过程与宏观过程的区别与联系的准确认识，使霍斯特曼的理论达到了这一新的高度。在化学热力学的形成过程中，F·马西厄、J·W·吉布斯和亥姆霍兹提出的热力学函数起到了重要作用。另一方面，van‘t Hoff利用半透膜的作用，重新引入了循环过程的方法。化学热力学的建立为不可逆热力学奠定了基础，不可逆热力学的第一步是1922年由De Donder提出的。

The main part in the formation process of physical chemistry was the establishment of chemical thermodynamics, which was closely related with the chemical kinetics.1. The theory of heterogeneous eqilibrium and that of dissociation equilibrium are to be supposed as the fundamental moments for the formation of chemical thermodynamics. G.Kirchhoff was the first to apply the principles of thermodynamics to sollutions in 1858. His theory was of much help to the studies by A.Horstmann, C.M.Guldberg, H.von Helmholtz and others.2.It was the theory of dissociation equilibrium that established the primary stage in the formation of chemical thermodynamics. In 1873 Horstmann, who is known to be the first chemist to have applied the second law of thermodynamics to chemical processes,attained a qualitatively high level of the theory concerning dissociation equilibrium, founding it on the entropy maximization principle. This new level of Horstmann's theory was made possible through his exact recognising of the inner connection of chemical processes with thermodynamic laws, and of the difference and the relation between microscopic processes and macroscopic ones.3. In the formation of chemical thermodynamics, the thermodynamic functions, introduced by F.Massieu, J.W.Gibbs and Helmholtz, played a important role. On the other hand, van't Hoff reintroduced the method of cyclic process, using the action of semiprmeable membrance.4. The establishment of chemical thermodynamics gave the fundamental basis to the irreversible thermodynamics, the initial step of which was gotten by De Donder in 1922.