The platinum does act as a middleman after all, through its formation of the monomolecular gaseous film.
Furthermore, it is also easy to see how a platinum catalyst can be poisoned. Suppose there are molecules to which the platinum atoms will cling even more tightly than to oxygen. Such molecules will replace oxygen wherever it is found on the film and will not themselves be replaced by any gas in the atmosphere. They are on the, platinum sur face to stay, and any catalytic action involving hydrogen or oxygen is killed.
Since it takes very little substance to form a layer merely one molecule thick over any reasonable stretch of surface, a catalyst can be quickly poisoned by impurities that are present in the working mixture of gases, even when those impurities are present only in trace amounts. . If this is all so, then anything which increases the amount of surface in a given weight of metal will also increase the catalytic efficiency. Thus, powdered platinum, with a great deal of surface, is a much more effective catalytic agent than the same weight of bulk platinum. It is perfectly fair, therefore, to speak of "surface catalysis."
But what is there about a surface film that hastens the process of, let us say, hydrogen-oxygen combination? We still want to remove the suspicion of magic.
To do so, it helps to recognize what catalysts can't do.
For instance, in the 187Ws, the American physicist Josiah Willard Gibbs painstakingly worked out the applica tion of the laws of thermodynamics to chemical reactions.
He showed that there is a quantity called "free energy" which always decreases in any chemical reaction that is spontaneous-that is, that proceeds without any input of energy.
Thus, once hydrogen and oxygen start reacting, they keep on reacting for as long as neither gas is completely used up, and as a result of the reaction water is formed. We explain this by saying that the free energy of the water is less than the free energy of the hydrogen-oxygen mixture.
The reaction of hydrogen and oxygen to form water is analogous to sliding down an "energy slope."
But if that is so, why don't hydrogen and oxygen mole cules combine with'each other as soon as they are mixed.
Why do they linger for indefinite periods at the top of the energy slope after being mixed, and react and slide down ward only after being heated?
Apparently, before hydrogen and oxygen molecules (each composed of a pair of atoms) can react, one or the other must be pulled apart into individual atoms. That requires an energy input. It represents an upward energy slope, before the downward slope can be entered. It is an "energy hump," so to speak. The amount of energy that must be put into a reacting system to get it over that energy hump is called the "energy of activation," and the con 207 cept was first advanced in 1889 by the Swedish chemist Svante August Arrhenius.
When hydrogen and oxygen molecules are colliding at ordinary temperature, only the tiniest fraction happen to possess enough energy of motion to break up on collision.
That tiniest fraction, which does break up and does react, then liberates enough energy, as it slides down the energy slope, to break up additional molecules. However, so little energy is produced at any one-time that it is radiated away before it can do any good. 'ne net result is that hydrogen and oxygen mixed at room temperature do not react. ff the temperature is raised, molecules move more rapidly and a larger proportion of them possess the nec essary energy to break up on collision. (More, in other words, can slide over the energy hump.) More and more energy is released, and there comes a particular tempera ture when more energy is released than can be radiated away. The temperature is therefore further raised, which produces more energy, which raises the temperature still further-and hydrogen and oxygen proceed to react with an explosion.
In 1894 the Russian chemist Wilhelm Ostwald pointed out that a catalyst could not alter the free energy relation ships. It cannot really make a reaction go, that would not go without it-though it can make a reaction go rapidly that in its absence would prciceed with only imperceptible speed.
In other words, hydrogen and oxygen combine in the absence of platinum but at an imperceptible rate, and the platinum baste-maker accelerates that combination. For water to decompose to hydrogen and oxygen at room tem perature (without the input of energy in the form of an electric current, for instance) is impossible, for that would mean spontaneously moving up an energy slope. Neither platinum nor any other catalyst could make a chemical reaction move up an energy slope. If we found one that did so, then that would be magic.
Or else we would have to modify the laws of thermodynamics.
But how does platinum hasten the reaction it does hasten? What does it do to the molecules in the film?
Ostwald's suggestion (accepted ever since) is that cata lysts hasten reactions by lowering the energy of activation of the reaction-flattening out the hump. At any given tem perature, then, more molecules can cross over the hump and slide downward, and the rate of the reaction increases, sometimes enormously.
For instance, the two oxygen atoms m an oxygen mole cule hold together with a certain, rather strong, attachment, and it is not easy to split them apart. Yet such splitting is necessary if a water molecule is to be formed.
When an oxygen atom is attached to a platinum atom and forms part of a surface film, however, the situation changes. Some of the bond-forming capabilities of the oxygen molecule are used up in forming the attachment to the platinum, and less is available for holding the two oxygen atoms together. The oxygen atom might be said to be "strained."
If a hydrogen atom happens to strike such an oxygen atom, strained in the film, it is more likely to knock it apart into individual oxygen atoms (and react with one of them) than would be the case if it collided with an oxygen atom free in the body of a gas. The fact that the oxygen molecule is strained means thaf it is easier to break apart, and that the energy of activation for the hyqrogen-oxygen combination has been lowered.
Or we can try a metaphor again. Imagine a brick resting on the upper reaches of a cement incline. The brick should, ideally, slide down the incline. To do so, however, it must overcome frictional forces which hold it in place against the pull of gravity. The frictional forces are here analogous to the forces holding the oxygen molecule together.
To overcome the frictional force one must give the brick an initial push (the energy of activation), and then it slides down.
Now, however, we will try a little "surface catalysis." We will coat the slide with wax. If we place the brick on top of such an incline, the merest touch will start it moving downward. It may move downward without any help from us at all.
In waxing the cement incline we haven't increased the force of gravity, or added energy to the system. We have merely decreased the frictional forces (that is, the energy, hump), and bricks can be delivered down such a waxed incline much more easily and much more rapidly than down an unwaxed incline.
So you see that on inspection, the magical clouds of glory fade into the light of common day, and the wonderful word "catalyst" loses all its glamor. In fact, notlfing is left to it but to serve as the foundation for virtually all of chemical industry and, in the form of enzymes, the founda tion of all of life, too.
And, come to think of it, that ought to be glory enough for any reasonable catalyst.
17. The Slowly Moving Finger
Alas, the evidences of mortality are all about us; the other day our little parakeet died. As nearly as we could make out, it was a trifle over five years old, and we had always taken the best of care of it. We had fed it, watered it, kept its cage clean, allowed it to leave the cage and fly about the house, taught it a small but disreputable vocabulary, perrffltted it to ride about on our shoulders and eat at will from dishes at the table. In short, we encouraged it to think of itself as one of us humans.