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化学 1918

气体在玻璃、云母与铂平面上的吸附

欧文·朗缪尔

气体只在固体上吸附一层分子那么深——而这单薄的一层,奠定了表面化学。

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In depth · the introduction

当气体黏到固体上时,它并不会越堆越高——它铺下恰好一层分子那么厚的一层,然后就停住了。

核心想法

把一块干净的表面放进气体里,总有一部分气体会黏上去。这早不是新闻。欧文·朗缪尔的洞见,关乎黏上去多少。他论证说,把气体分子按在固体上的力,短程到只能抓住直接挨着表面的那些分子。叠在第一层之上的第二个分子,几乎什么也感觉不到。于是这层黏附物只有一层分子那么深——一层漆,绝不会有两层。

从这一幅图,他得到了一条干净的规则。把表面想成一排座位。气体分子不断落进空座,落座的分子又不断起身离开。把气体压强往上推,更多座位被坐满——但只能填到这排座位坐满为止。被占座位的比例,沿着一条利落的曲线走:先快速上升,再在「满座」处变平。这条曲线就是朗缪尔等温线,也是表面化学的根基。

它是如何诞生的

朗缪尔是个不寻常的人物:他不是大学教授,而是纽约州斯克内克塔迪通用电气研究实验室里的一名工业科学家,受雇去弄清灯泡灯丝为何会烧断。在追究灼热金属丝、以及丝上那层薄薄的气膜如何行事的过程中,他被卷入了一个更深的问题:气体究竟是怎样与固体相遇的——而他带着一个实验家对极低压下洁净测量的执着。

1918 年的论文,正是由此而来。它如此富有成果,以致在 1932 年帮他成为第一位出身工业界、而非大学的诺贝尔化学奖得主。许多表面工作,是他与凯瑟琳·布洛杰特一同完成的——「朗缪尔—布洛杰特膜」之名里留着她,那正是从这项研究里直接长出来的;她后来还发明了用于相机镜头与眼镜的无反射玻璃。

它为何重要

几乎一切有用的事,都发生在表面上:催化剂在它的表面上加速反应,活性炭滤芯在它的表面上截住气味,传感器靠黏上它表面的东西来探测气体。在朗缪尔之前,「黏到表面上」是个含糊的概念;在他之后,它成了一个你能预测、能测量、能据以设计的数字。他那条方程,至今仍是化学家弄清一份粉末有多大表面、一种催化剂会如何行事、一个滤芯能容纳多少污染物的办法。

一个可以想象的画面

想象一个车位数量固定的停车场。车(气体分子)不断驶入,也不断驶离。车流稀少时,几乎每辆来的车都能找到位子,于是车场大致随来车的多少同步填满。可一旦挤起来,新来的车越来越常发现位子全满、只好开走。车场永远不会超过「满」——而关键是,你没法把车叠到车上。这「先一层、然后满」,正是朗缪尔的表面,而那条填充曲线,就是他的等温线。

可交互的朗缪尔吸附等温线:一个滑块升高气体压强,另一个设定气体黏附得多强;曲线与一格格表面位点先快速填满、再随单层饱和而趋于平坦。

它的位置

这是表面化学的诞生,它立足于本馆已有的道尔顿、阿伏伽德罗与路易斯的原子图景,也立足于吉布斯的平衡思想。引人注目的是,同样这条 S 形的饱和曲线,五年前就在生物学里出现过——米氏酶动力学定律,本馆也有——因为两者讲的是同一个故事:东西填满一组固定的位点。朗缪尔的单分子层,后来被 BET 理论叠成多层,而那正是表面积至今的测量之法。

The original document
Original source text
Irving Langmuir · J. Am. Chem. Soc. 40 (1918) 1361–1403 · "The Adsorption of Gases on Plane Surfaces of Glass, Mica and Platinum"
The single-layer postulate
[Editorial summary] Langmuir opens by arguing that the forces holding a gas onto a solid are short-ranged — essentially the same valence forces that bind atoms in molecules, reaching out only about a molecular diameter. From this one premise a sharp conclusion follows: an adsorbed gas film, in most cases, can be only one molecule thick. The surface offers a fixed number of sites, and once a site is occupied the molecule above it lies beyond the reach of the surface's grip.
Adsorption as a dynamic balance
[Editorial summary] He then treats adsorption not as a static coating but as a continuous traffic: gas molecules strike the surface and stick to bare sites at a rate set by the pressure, while adsorbed molecules are forever evaporating back off. Equilibrium is the standstill where the two rates match — not an empty or a full surface, but a steady covered fraction that the molecules constantly turn over.
The isotherm
[Editorial summary] Setting the rate of condensation onto empty sites equal to the rate of evaporation from filled ones yields his isotherm: the fraction θ of the surface covered is bP/(1+bP), where P is the gas pressure and b measures how strongly the gas binds. The curve rises almost linearly at low pressure, bends over, and flattens toward θ = 1 as the single layer fills — the saturation that ordinary 'condensation' pictures could not explain. Langmuir checks this shape against his careful low-pressure measurements on glass, mica and platinum.
Mixtures, dissociation and reaction
[Editorial summary] The paper extends the same bookkeeping to several gases competing for the same sites, to molecules that split into two fragments on adsorbing (each needing a site), and to the way a surface that holds reactants is the stage on which catalysis happens — the seed of what became the Langmuir–Hinshelwood picture of surface reactions.
[ … ]
General Electric Research Laboratory, Schenectady · 1918