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化学 1876

论非均相物质的平衡

约西亚·威拉德·吉布斯

让自由能取极小,便能预言每一种相、混合与化学平衡。

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In depth · the introduction

水为何在一个固定的温度结冰?糖为何只能溶到某个限度?电池又为何不多不少推出那么多伏特?吉布斯找到了藏在这一切背后的同一条记账规则。

核心想法

每一种化学情形——冰在融化、糖在溶解、铁在生锈——都在朝着某个平衡漂移。吉布斯指出,有一个量,今天叫作自由能,系统总会把它降到不能再低;当它再也沉不下去时,系统便达到了平衡,不再变化。

从这一个想法里,他抽出了一条简单得惊人的计数法则——相律。对一种纯物质,你还能自由改变的条件数目——温度、压强——等于成分的数目,减去当前存在的相数,再加二。它在你做任何实验之前,就告诉你一份混合物有多少自由。

它是如何诞生的

约西亚·威拉德·吉布斯是耶鲁一位言语温和的教授,几乎从不离开纽黑文。1875 到 1878 年间,他在一份少有人读的康涅狄格学报上,发表了一篇三百页的论著,用的是冷峻而难啃的数学。几乎没有人读它。

英国的麦克斯韦,是极少数看出其深度的人之一。他用石膏雕出吉布斯的「热力学曲面」,把模型越过大西洋寄到了耶鲁。这部作品一直被埋没,直到被译成德文(1892)与法文(1899)——化学家们这才意识到,一位沉默的美国人,早已写下了他们这门学科的根基。

它为何重要

在吉布斯之前,化学在很大程度上是配方与经验法则。他把它变成了一门可预测的科学:给定温度、压强与用量,你如今便能算出一个反应往哪个方向走、能走多远、哪些相能共处一处——而不必无尽地试错。炼钢、生长半导体、配制药物,以及岩石的化学,全都跑在他的方程之上。

一个可以想象的画面

想象一片起伏的丘陵与谷地,化学系统每一个可能的状态,都是地形上的一个点,而「高度」就是它的自由能。无人打扰时,系统便顺坡下滚,落进它够得着的最低谷底——这就是平衡。改变温度或压强,你就让整片地形倾斜,于是最低的谷底也随之移动:0 °C 以下,冰的谷胜出;0 °C 以上,则是液态水的谷。吉布斯交给我们的,是这张地图,以及它如何倾斜的规则。

可交互的水压强—温度相图:选择固、液、气某一区域,或熔化/沸腾/升华某条线,或三相点,看共存几个相、还剩多少自由度 F = C − P + 2。

它的位置

卡诺(1824)与克劳修斯,曾为热机建起热力学;吉布斯则把它带进了化学。他与玻尔兹曼(1877)并肩而立——后者恰在同一时期,为熵赋予分子的含义;数十年后,吉布斯本人又写下了把这两股线索熔为一体的统计力学教科书。他所定义的那个自由能,正是每个化学学生如今都会以「ΔG」之名遇见的那个 G。

The original document
Original source text
J. Willard Gibbs · Transactions of the Connecticut Academy of Arts and Sciences, vol. III (1875–78): 108–248, 343–524
Die Energie der Welt ist constant. Die Entropie der Welt strebt einem Maximum zu.
The two sentences from Clausius that Gibbs set as the motto at the head of the memoir: “The energy of the world is constant. The entropy of the world tends toward a maximum.” The whole work is an answer to the question they pose — what configuration does matter settle into when its entropy can rise no further.
The criterion of equilibrium
Gibbs takes the two laws of thermodynamics as his only premises. For an isolated system he states the condition for equilibrium: among all variations that conserve the energy, the entropy is a maximum (equivalently, at fixed temperature and pressure the appropriate free energy is a minimum). Every later result is squeezed out of this single principle.
The fundamental equation and the potentials
He writes the energy of a homogeneous mass as a function of its entropy, volume and the masses of its independent components, and introduces for each component a quantity he calls its potential — what is now the chemical potential. Two phases in contact are in equilibrium only when their temperature, their pressure and the potential of every component are equal.
On coexistent phases
In this part Gibbs gives the modern thermodynamic meaning of the word phase, and by counting the equalities that must hold among r coexistent phases of n components he obtains the rule for the number of their independent variations — the phase rule, F = C − P + 2.
[ … ]
The memoir runs on to dilute solutions and osmotic pressure, the conditions of chemical reaction, electrochemical equilibrium, and the thermodynamics of surfaces and adsorption — a single framework for equilibria across phases, mixtures, reactions and interfaces.
New Haven, Connecticut · 1875–1878