Part II Of Other Things 15. Welcome, Stranger!
There are fashions in science as in everything else. Con duct an experiment that brings about an unusual success and before you can say, "There are a dozen imitations!" there are a dozen imitations!
Consider the element xenon (pronounced zee'non), dis covered in 1898 by William Ramsay and Morris William Travers. Like other elements of the same type it was iso lated from liquid air. The existence of these elements in air had remained unsuspected through over a century of ardent chemical analysis of the air, so when they finally dawned upon the chemical consciousness they were greeted as strange and unexpected newcomers. Indeed, the name, xenon, is the neutral form of the Greek word for "strange," so that xenon is "the strange one" in all literalness.
Xenon belongs to a group of elements commonly known as the "inert gases" (because they are chemically inert) or the "rare gases" (because they are rare), or "noble gases" because the standoffishness that results from chemi cal inertness seems to indicate a haughty sense of seff importance.
Xenon is the rarest of the stable inert gas and, as a matter of fact, is the rarest of all the stable elements on Earth. Xenon occurs only in the atmosphere, and there it makes up about 5. 3 parts per million by weight. Since the atmosphere weighs about 5,500,000,000,000,000 (five and a half quadrillion) tons, this means that the planetary supply of xenon comes to just about 30,000,000,000 (thirty billion) tons. This seems ample, taken in full, but picking xenon atoms out of the overpoweringly more corn,mon constituents of the atmosphere is an arduous task and so xenon isn't a common substance and never will be.
What with one thing and another, then, xenon was not a popular substance in the chemical laboratories. Its chem ical, physical, and nuclear properties were worked out, but beyond that there seemed little worth doing with it. It remained the little strange one and received cold shoulders and frosty smiles.
Then, in 1962, an unusual experiment involving xenon was announced whereupon from all over the world broad smiles broke out across chemical countenances, and little xenon was led into the test tube with friendly solicitude.
"Welcome, stranger!" was the cry everywhere, and now you can't open a chemical journal anywhere without find ing several papers on xenon.
What happened?
If you expect a quick answer, you little know me. Let me take my customary route around Robin Hood's barn and begin by stating, first of all, that xenon is a gas.
Being a gas is a matter of accident. No substance is a gas intrinsically, but only insofar as temperature dictates.
On Venus, water and ammonia are both gases. On Earth, ammonia is a gas, but water is not. On Titan, neither am monia nor water are gases.
So I'll have to set up an arbitrary criterion to suit my present purpose. Let's say that any substance that remains a gas at -1000 C. (-148' F. ) is a Gas with a capital letter, and concentrate on those. This is a temperature that is never reached on Earth, even in an Antarctic winter of extraordinary severity, so that no Gas is ever anything but gaseous on Earth (except occasionally in chemical lab oratories).
Now why is a Gas a Gas?
I can start by saying that every substance is made up of atoms, or of closely knit groups of atoms, said groups being called molecules. There are attractive forces between atoms or molecules which make them "sticky" and tend to hold them together. Heat, however, lends these atoms or molecules a certain kinetic energy (energy of motion) which tends to drive them apart,. since each atom or mole cule has its own idea of where it wants to go. [I enjoy sin]
The attractive forces among a given set of atoms or molecules are relatively constant, but the kinetic energy varies with the temperature. Therefore, if the temperature is raised high enough, any group of atoms or molecules will fly apart and the material becomes a gas. At tempera tures over 60000 C. all known substances are gases.
Of course, there are only a, few exceptional substances with interatomic or intermolecular forces so strong that it takes 6000' C. to overcome them. Some substances, on the other hand, have such weak intermolecular attractive forces that the warmth of a summer day supplies enough kinetic energy to convert them to gas (the common anes thetic, ether, is an example).
Still others have intermolecular attractive forces so much weaker still that there is enough heat at a tempera ture of -I 00' C. to keep them gases, and it is these that are the Gases I am talking about.
The intermolecular or interatomic forces arise out of the distribution of electrons within the atoms or molecules.
The electrons are distributed among various "electron shells," according to a system we can,accept without de tailed explanation. For instance, the aluminum atom con tains 13 electrons, which are distributed as follows: 2 in the innermost shell, 8 in the next shell, and 3 in the next shell. We can therefore signify the electron distribution in the aluminum atom as 2,8,3.
The most stable and symmetrical distribution of the electrons among the electron shells is that distribution in which the outermost shell holds either all the electrons it can hold, or 8 electrons-whichever is less. The innermost electron shell can hold only 2, the next can hold 8, and each of the rest can hold more than 8. Except for the situ ation where only the innermost shell contains electrons, * No, I am not implying that atoms know what they are doing and have consciousness. This is just my teleological way of talk ing. Teleology is forbidden in scientific'articies, 1-ut it s'o happens then, the stable situation consists of 8 electrons in the outermost shell.
There are exactly six elements known in which this situ ation of maximum stability exists:
Electron Electron Element Symbol Distribution Total helium He 2 2 neon Ne 2,8 10 argon Ar 2,8,8 is krypton Kr 2,8,18,8 36 xenon Xe 2,8,18,18,8 54 radon Rn 2,8,18,32,18,8 86
Other atoms without this fortunate electronic distribu tion are forced to attempt to achieve it by grabbing addi tional electrons, or getting rid of some they already pos sess, or sharing electrons. In so doing, they undergo chem ical reactions. The atoms of the six elements listed above, however, need do nothing of this sort and are sufficient unto themselves. They have no need to shift electrons in any way and that means they take part in no chemical reactions and are inert. (At least, this is what I would have said prior to 1962. )
The atoms of the inert gas family listed above are so self-sufficient, in fact, that the atoms even ignore one another. There is little interatomic attraction, so that all are gases at room temperature and all but radon are Gases.
To be sure, there is some interatomic attraction (for no atoms or molecules exist among which there is no attrac tion at all). If one lowers the temperature sufficiently, a point is reached where the attractive forces become dom inant over the disruptive effect of kinetic energy, and every single one of the inert gases will, eventually, become an inert liquid.
What about other elements? As I said, these have atoms with electron distributions of less than maximum stability and each has a tendency to alter that distribution in the direction of stability. For instance, the sodium atom (Na) has a distribution of 2,8, I. If it could get rid of the outer most electron, what would be left would have the stable 2 8 configuration of neon. Again, the chlorine atom (CI) [email protected]/* */ a distribution of 2,8,7. If it could gain an electron, it would have the 2,8,8 distribution of argon.
Consequently, if a sodium atom encounters a chlorine atom, the transfer of an electron from the sodium atom to the chlorine atom satisfies both. However, the loss of a negatively charged electron leaves the sodium atom with a deficiency of negative charge or, which is the same thing, an excess of positive charge. It becomes a positively charged sodium ion (Na+). The chlorine atom, on the other band, gaining an electron, gains an excess of nega tive charge and becomes a negatively charged chloride ion ["chlorine ion" as a convention of chemi amp;al nomenclature we might just as well accept with a weary sigh. Anyway, the "d" is not a typographical error] (CI-).
Opposite charges attract, so the s
odium ion attracts all the chloride ions within reach and vice versa. These strong attractions cannot be overcome by the kinetic energy in duced at ordinary temperatures, and so the ions hold to gether firmly enough for "sodium chloride" (common salt) to be a solid. It does not become a gas, in fact, until a temperature of 1413' C. is reached. . Next, consider the carbon atom (C). Its electron dis tribution is 2,4. If it lost 4 electrons, it would gain the 2 helium configuration; if it gained 4 electrons, it would gain the 2,8 neon configuration. Losing or gaining that many electrons is not easy,_so the carbon atom shares electrons instead. It can, for instance, contribute one of its electrons to a "shared pool" of two electrons, a pool to which a neighboring carbon atom also contributes an elec tron. With its second electron it can form another shared pool with a second neighbor, and with its third and fourth, two more pools with two more neighbors. Each neighbor * The charged chlorine atom is called "chloride ion" and not ran set up additional pools with other neighbors. In this way, each carbon atom is surrounded by four other carbon atoms.
These shared electrons fit into the outermost electron shells of each carbon atom that contributes. Each carbon atom has 4 electrons of its own in that outermost shell and 4 electrons contributed (one apiece) by four neighbors.
Now, each carbon atom has the 2,8 configuration of neon, but only at the price of remaining close to its neighbors.
The result is a strong interatomic attraction, even though electrical charge is not involved. Carbon is a solid'and is not a gas until a temperature of 42000 C. is reached.
The atoms of metallic elements also stick together ,strongly, for similar reasons, so that tungsten, for instance, is not a gas until a temperature of 59000 C. is reached.
We cannot, then, expect to have a Gas when atoms achieve stable electron distribution by transferring elec trons in such a manner as to gain an electric charge; or by sharing electrons in so complicated a fashion that vast numbers of atoms stick together in one piece.
What we need is something intermediate. We need a situation where atoms achieve stability by sharing electrons (so that no electric charge arises) but where the total number of atoms involved in the sharing is very small so that only small molecules result. Within the molecules, attractive forces may be large, and the molecules may not be shaken apart without extreme temperature. The attrac tive forces between one molecule and its neighbor, how ever, may be smafl-and that will do.
Let's consider the hydrogen atom, for instance. It has but a single electron. Two hydrogen atoms can each con tribute its single electron to form a shared pool. As long as they stay together, each can count both electrons in its outermost shell and each will have the stable helium configuration. Furthermore, neither hydrogen atom will have any electrons left to form pools with other neighbors, hence the molecule will end there. Hydrogen gas will con sist of two-atom molecules (H2) The attractive force between the atoms in the molecule is large, and it takes temperatures of more than 20001 C. to shake even a small fraction of the hydrogen molecules into single atoms. There will, however, be only weak at tractions among separate hydrogen molecules, each of which, under the new arrangement, will have reached a satisfactory pitch of self-sufficiency. Hydrogen, therefore, will be a Gas not made up of separate atoms as is the case with the inert gases, but of two-atom molecules.
Something similar will be true in the case of fluorine (electronic distribution 2,7), oxygen (2,6) and nitrogen (2,5). The fluorine atom can contribute an electron and form a shared pool of two electrons with a,neighboring fluorine atom which also contributes an electron. Two oxygen atoms can contribute two electrons apiece to form a shared pool of four electrons, and two nitrogen atoms can contribute three electrons each and form a shared pool of six electrons.
I In each case, the atoms will achieve the 2,8 distribution of neon at the cost of forining paired molecules. As a result, enough stability is achieved so that fluorine (F2). oxygen (02), and nitrogen (N2) are all Gases.
The oxygen atom can also form a shared pool of two electrons with each of two neighbors, and those two neigh bors can form another shared pool of two electrons among themselves. The result is a combination of three oxygen atoms (O:j), each with a neon configuration. This com bination, 03, is called ozone, and it is a Gas too.
Oxygen, nitrogen, and fluorine can form mixed mole cules, too. For instance, a nitrogen and an oxygen atom can combine to achieve the necessary stability for each.
Nitrogen may also form shared pools of two electrons with each of three fluorine atoms, while oxygen may do so with each of two. The resulting compounds: nitrogen oxide (NO), nitroen trifluoride (NF3), and oxygen di fluoride (OF2) are all Gases.
Atoms which, by themselves, will not form Gases may do so if combined with either hydrogen, oxygen, nitrogen, or fluorine. For instance, two chlorine atoms (2,8,7, re member) will form a shared pool of two electrons so that ,both achieve the 2,8,8 argon configuration. Chlorine (CI2) is therefore a gas at room temperature-with intermolecu lar attractions, however, large enough to keep it from be ing a Gas, Yet if a chlorine atom forms a shared pool of two electrons with a fluorine atom, the result, chlorine fluoride (CIF), is a. Gas.
The boron atom (2,3) can form a shared pool of two electrons with each of three fluorine atoms, and the carbon atom a shared pool of two electrons with each of four fluorine atoms. The resulting compounds, boron trifluoride (BF3) and carbon tetrafluoride (CF4), are Gases.
A carbon atom can form a shared pool of two elec trons with each of four hydrogen atoms, or a shared pool of four electrons with an oxygen atom, and the resulting compounds, methane (CH-4) and carbon monoxide (CO), are gases. A two-carbon combination may set up a shared pool of two electrons with each of four hydrogen atoms (and a shared pool of four electrons with one another); a silicon atom may setup a shared pool of two electrons with each of four hydrogen atoms. The compounds, ethylene (C2H4) and silane (SiH4), are Gases.
Altogether, then, I can list twenty Gases which fall into the following categories:
(1) Five elements made up of single atoms: helium, neon, argon, krypton, and xenon.
(2) Four elements made up of two-atom molecules: hydrogen, nitrogen, oxygen, and fluorine.
(3) One element form made up of three-atom mole cules: ozone (of oxygen).
(4) Ten compounds, with molecules built up of two different elements, at least one of which falls into category (2).
The twenty Gases are listed in order of increasing boil ing point in the accompanying table, and that boiling point is given in both the Celsius scale (' C. ) and the Absolute scale (' K. ).
The five inert gases on the list are scattered among the fifteen other Gases. To be sure, two of the three lowest 192 boiling Gases are helium and neon, but argon is seventh, krypton is tenth, and xenon is seventeenth. It would not be surprising if all the Gases, then, were as inert as the inert gases.
The Twenty Gases
Substance Fori ula B. P. (C. -) B. P. (K. -)
Helium He -268. 9 4. 2
Hydrogen H, -252. 8 20. 3
Neon Ne -245. 9 27. 2
Nitrogen N, -195. 8 77. 3 f
Carbon monoxide '-O -192 81
Fluorine F2 -188 85
Argon Ar -185. 7 87. 4
Oxygen 0, -183. 0 90. 1
Methane CH4 -161. 5 111. 6
Krypton Kr -152. 9 120. 2
Nitrogen oxide NO -151. 8 121. 3
Oxygen difluoride OF, -144. 8 128. 3
Carbon tetrafluoride CF, -128 145
Nitrogen trifluoride NF3 -120 153
Ozone 0, -111. 9 161. 2
Silane SiH, -111. 8 161. 3
Xenon Xe -107. 1 166. 0
Ethylene C,H, -103. 9 169. 2
Boron trifluoride BF, -101 172
Chlorine fluoride CIF -100. 8 172. 3
Perhaps they might be at that, if the smug, self-sufficient molecules that made them up were permanent, unbreak able affairs, but they are not. All t
he molecules can be broken down under certain conditions, and the free atoms (those of fluorine and oxygen particularly) are active in deed.
This does not show up in the Gases themselves. Sup pose a fluorine molecule breaks up,into two fluorine atoms, and these find themselves surrounded only by fluorine molecules? The only possible result is the re-formation of a fluorine molecule, and nothing much has happened. If, however, there are molecules other than fluorine present, a new molecular combination of greater stability than F2 is possible (indeed, almost certain in the case of fluorine), and a chemical reaction results.
The fluorine molecule does have a tendency to break apart (to a very small extent) even at ordinary tempera tures, and this is enough. The free fluorine atom will attack virtually anything n. on-fluorine in sight, and the heat of reaction will raise the temperature, which will bring about a more extensive split in fluorine molecules, and so on. The result is that molecular fluorine is the most chemically active of all the Gases (with chlorine fluoride almost on a par with it and ozone making a pretty good third).
The oxygen molecule is torn apart with greater diffi culty and therefore remains intact (and inert) under con ditions where fluorine will not. You may think that oxygen is an active element, but for the most part this is only true under elevated temperatures, where more energy is avail able to tear it apart. After all, we live in a sea of free oxygen without damage. Inanimate substances such as pa per, wood, coal, and gasoline, all considered flammable, can be bathed by oxygen for indefinite periods without perceptible chemical reaction-until heated.
Of course, once heated, oxygen does become active and combines easily with other Gases such as hydrogen, carbon monoxide, and methane which, by that token, can't be considered particularly inert either.
The nitrogen molecule is torn apart with still more diffi culty and, before the discovery of the inert gases, nitrogen was the inert gas par excellence. It and carbon tetrafluoride are the only Gases on the list, other than the inert gases themselves, that are respectably inert, but even they can be torn apart.
Life depends on the fact that-certain bacteria can split the nitrogen molecule; and important industrial processes arise out of the fact that man has learned to do the same thing on a large scale. Once the nitrogen molecule is torn apart, the individual nitrogen atom is quite active, bounces around in all sorts of reactions and- in fact, is the fourth most common atom in living tissue and is essential to all its workings.
In the case of the inert gases, all is different. There are no molecules to pull apart. We are dealing with the self sufficient atom itself, and there seemed little likelihood that combination with any other atom would produce a situa tion of greater stability. Attempts to get inert gases to form compounds, at the time they were discovered, failed, and chemists were quickly satisfied that this made sense.
To be sure, chemists continued to try, now and again, but they also continued to fail. Until 1962, then, the only successes chemists had had in tying the inert. gas atoms to other atoms was in the formation of "clathrates. " In a clathrate, the atoms making up a molecule form a cage like structure and, sometimes, an extraneous atom-even an inert gas atom-is trapped within the cage as it forms.
The inert gas is then tied to the substance and cannot be liberated without breaking down the molecule. However, the inert gas atom is only physically confined; it has not formed a chemical bond.
And yet, let's reason things out a bit. The boiling point of helium is 4. 2' K. ; that of neon is 27. 20 K. , that of argon 87. 4' K. , that of krypton 120. 2' K. , that of xenon 166. 0' K. The boiling point of radon, the sixth and last inert gas and the one with the most massive atom, is 211. 3- K. (-61. 8- C. ) Radon is not even a Gas, but merely a gas.
Furthermore, as the mass of the inert gas atoms in creases, the ionization potential (a quantity which meas ures the ease with which an electron can be removed alto gether from a particular atom) decreases. The increasing boiling point and decreasing ionization potential both indi cate that the inert gases become less inert as the mass of the individual atoms rises.
By this reasoning, radon would be the least inert of the inert gases and efforts to form compounds should concen trate upon it as offering the best chance. However, radon is a radioactive element with a half-life of less than four days, and is so excessively rare that it can be worked with only under extremely specialized conditions. The next best bet, then, is xenon. This is very rare, but it is available and it is, at least, stable.
Then, if xenon is to form a chemical bond, with what other atom might it be expected to react? Naturally, the most logical bet would be to choose the most reactive sub stance of all-fluorine or some fluorine-containing com pound. If xenon wouldn't react with that, it wouldn't react with anything.
(This may sound as though I am being terribly wise after the event, and I am. However, there are some who were legitimately wise. I am told that Linus Pauling rea soned thus in 1932, well before the event, and that a gentleman named A. von Antropoff did so in 1924. )
In 1962, Neil Bartlett and others at the University of British Columbia were working with a very unusual com pound, platinum hexafluoride (PtF6). To their surprise, they discovered that it was a particularly active compound.
Naturally, they wanted to see what it'could be made to do, and one of the thoughts that arose was that here might be something that could (just possibly) finally pin down an inert gas atom.
So Bartlett mixed the vapors of PtF6 with xenon and, to his astonishment, obtained a compound which seemed to be XePtFc,, xenon platinum hexafluoride. The announce ment of this result left a certain area of doubt, however.
Platinum hexafluoride was a sufficiently complex compound to make it just barely possible that it had formed a clath rate and trapped the xenon.
A group of chemists at Argonne National Laboratory in Chicago therefore tried the straight xenon-plus-fluorine experiment, heating one part of xenon with five parts of fluorine under pressure at 400' C. in a nickel container.
They obtained xenon tetrafluoride (XeF4), a straightfor ward compound of an inert gas, with no possibility of a clathrate. (To be sure, this experiment could have been tried years before, but it is no disgrace that it wasn't. Pure xenon is very hard to get and pure fluorine is very danger ous to handle, and no chemist could reasonably have been expected to undergo the expense and the risk for so slim-chanced a catch as an inert gas compound until after Bartlett's experiment had increased that "slim chance" tremendously. )
And once the Argonne results were announced, all Hades broke loose. It. looked as though every inorganic chemist in the world went gibbering into the inert gas field. A whole raft of xenon compounds, including not only XeF4, but also XeF. , XeF6, XeOF2, XeOF3, XeOF4, XeO3, H4XeO4, and H,XeO,, have been reported.
Enough radon was scraped together to form radon tetra fluoride (RnF4). Even krypton, which is more inert than xenon, has been tamed, and krypton difluoride (KrF2) and krypton tetrafluoride (KrF4) have been formed.
The remaining three inert gases, argon, neon, and helium (in order of increasing inertness), as yet remain untouched.
They are the last of the bachelors, but the world of chemis try has the sound of wedding bells ringing in its ears, and it is a bad time for bachelors.
As an old (and cautious) married man, I can only say to this-no comment.