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反应速度与宏观热力学函数之间在数值上并无联系。能使二者关联的是所谓平衡条件:(a) sum from χ_iμ_i产-sum from χ_iμ_i反=0,(b)净反应速度的R=-θ{sum from χ_iμ_i产-sum from χ_iμ_i反}=0,以及将反应速度常数与化学平衡常数联系起来的关系式 K=K_f/K_b (1)式中,K为平衡常数,K_f、K_b分别为正、逆向反应速度常数。作为联系化学动力学与化学热力学之间的桥梁,这个关系式一直为人们所重视。然而,该式是不完善的。虽然所有的化学反应都可以满足平衡条件,但却未必能同时满足(1)式中所示的关系。本文将讨论这个关系式的局限性,导出化学平衡常数与反应速度常数之问的广义关系式,并根据广义关系式提出热力学对反应速度定律的限制。
There is no numerical connection between the reaction rate and the macro-thermodynamic function. The relationship between the two is the so-called equilibrium conditions: (a) sum from χ_iμ_i production-sum from χ_iμ_i anti = 0, (b) net reaction rate R = -θ {sum from χ_iμ_i production-sum from χ_iμ_i anti} = 0 , And the relationship between the reaction rate constant and the chemical equilibrium constant K = K_f / K_b (1) where K is an equilibrium constant, and K_f and K_b are positive and negative reaction rate constants, respectively. As a link between chemical kinetics and chemical thermodynamics, this relationship has always been valued. However, this formula is imperfect. Although all the chemical reactions can satisfy the equilibrium conditions, they may not satisfy the relationship shown in (1) at the same time. This article will discuss the limitations of this relation and derive the generalized relation between the chemical equilibrium constant and the reaction rate constant. According to the generalized relation, the thermodynamic limit on the reaction rate law is proposed.