Volume 1: Electricity from Isotopes

In 1902 Rutherford and his co-worker Frederick Soddy (1877-1956) showed that when uranium atoms gave off alpha particles, a new kind of atom was formed that was not uranium at all. It was this new atom that was eventually found to give off a beta particle, and then another atom of still another element was formed. This work of Rutherford and Soddy began a line of investigation that by 1907 had shown that there was a whole radioactive chain of elements, each one breaking down to the next in line by giving off either an alpha particle or a beta particle, until finally a lead atom was formed that was not radioactive.

There was, in short, a “radioactive series” beginning with uranium (atomic number 92) and ending with lead (atomic number 82). The same was true of thorium (atomic number 90), which began a series that also ended with lead. Still a third element, actinium (atomic number 89) was, at that time, the first known member of a series that also ended in lead.

The various atoms formed in these three radioactive series were not all different in every way. When the uranium atom gives off an alpha particle, it forms an atom originally called “uranium X₁”. On close investigation, it turned out that this uranium X₁ had the chemical properties of thorium. Uranium X₁, had, however, radioactive properties different from ordinary thorium.

Uranium X₁ broke down so rapidly, giving off beta particles as it did so, that half of any given quantity would have broken down in 24 days. Another way of saying this (which was introduced by Rutherford) was that the “half-life” of uranium X₁, is 24 days. Ordinary thorium, however, gives off alpha particles, not beta particles, and does so at such a slow rate, that its half-life is 14 billion years!

Uranium X₁, and ordinary thorium were in the same place in the list of elements by chemical standards, and yet there was clearly something different about the two.

Here is another case. In 1913 the British chemist Alexander Fleck (1889- ) studied “radium B” and “radium D”, the names given to two different kinds of atoms in the uranium radioactive series. He also studied “thorium B” in the thorium radioactive series and “actinium B” in the actinium radioactive series. All four are chemically the same as ordinary lead; all four are in the same place in the list of elements. Yet each is different from the radioactive standpoint. Though all give off beta particles, radium B has a 38half-life of 27 minutes, radium D one of 19 years, thorium B one of 11 hours, and actinium B one of 36 minutes.

In 1913 Soddy called atoms that were in the same place in the list of elements, but which had different radioactive properties, “isotopes”, from Greek words meaning “same place”.

At first, it seemed that the only difference between isotopes might be in their radioactive properties and that only radioactive atoms were involved. Quickly that proved not to be so.

It proved that it was possible to have several forms of the same element that were all different even though none of them were radioactive. The uranium series, the thorium series, and the actinium series all ended in lead. In each case the lead formed was stable (not radioactive). Were the lead atoms identical in every case? Soddy had worked out the way in which atomic weights altered every time an alpha particle or a beta particle was given off by an atom. Working through the three radioactive series he decided that the lead atoms had different atomic weights in each case.

The uranium series ought to end with lead atoms that had an atomic weight of 206. The thorium series ought to end in lead atoms with an atomic weight of 208 and the actinium series in lead atoms with an atomic weight of 207.

If this were so, there would be 3 lead isotopes that would differ not in radioactive properties, but in atomic weight. The isotopes could be referred to as lead-206, lead-207, and lead-208. If we use the chemical symbol for lead (Pb), we could write the isotopes, ²⁰⁶Pb, ²⁰⁷Pb, and ²⁰⁸Pb. (We read the symbol ²⁰⁶Pb as lead-206.) Atomic weight measurements made in 1914 by Soddy and others supported that theory.

All 3 lead isotopes had the same atomic number of 82. The atoms of all 3 isotopes had nuclei with an electric charge of +82 and all 3 had 82 electrons in the atom to balance that positive nuclear charge. The difference was in the mass of the nucleus only.

But what of ordinary lead that existed in the rocks far removed from any radioactive substances and that had presumably been stable through all the history of earth? Its atomic weight was 207.2.

Was the stable lead that had no connection with radioactivity made up of atoms of still another isotope, one with a fractional atomic weight? Or could stable lead be made up of a mixture of isotopes, each of a different whole-number atomic weight and was the overall atomic weight a fraction only because it was an average?

It was at the moment difficult to tell in the case of lead, but an answer came in connection with another element, the rare gas neon (atomic symbol Ne), which has an atomic weight of 20.2.

Was that fractional atomic weight something that was possessed by all neon atoms without exception or was it the average of some lightweight atoms and some heavyweight ones? It would be a matter of crucial importance if isotopes of neon could be found, for neon had nothing to do with any of the radioactive series. If neon had isotopes then any element might have them.

In 1912 Thomson was working on neon. He sent a stream of cathode-ray electrons through neon gas. The electrons smashed into the neon atoms and knocked an electron off some of them. That left a neon ion carrying a single positive charge—an ion that could be written Ne⁺.

The neon ions move in the electric field as electrons do, but in the opposite direction since they have an opposite charge. In the combined presence of a magnet and of an electric field, the neon ions move in a curved path. If all the neon ions had the same mass, all would follow the same curve. If some were more massive than others, the more massive ones would curve less.

The neon ions ended on a photographic plate, which was darkened at the point of landing. There were two regions of 41darkening, because there were neon ions of two different masses that curved in two different degrees and ended in two different places. Thomson showed, from the amount of curving, that there was a neon isotope with an atomic weight of 20 and one with an atomic weight of 22—²⁰Ne and ²²Ne.

What’s more, from the intensity of darkening, it could be seen that ordinary neon was made up of atoms that were roughly 90% ²⁰Ne and 10% ²²Ne. The overall atomic weight of neon, 20.2, was the average atomic weight of these 2 isotopes.

Thomson’s instrument was the first one capable of separating isotopes and such instruments came to be called “mass spectrometers”. The first to use the name was the English physicist Francis William Aston (1877-1945), who built the first efficient instrument of this type in 1919.

He used it to study as many elements as he could. He and those who followed him located many isotopes and determined the frequency of their occurrence with considerable precision. It turned out, for instance, that neon is actually 90.9% ²⁰Ne, and 8.8% ²²Ne. Very small quantities of still a third isotope, ²¹Ne, are also present, making up 0.3%.

As for ordinary lead in nonradioactive rocks, it is made up of 23.6% ²⁰⁶Pb, 22.6% ²⁰⁷Pb, and 52.3% ²⁰⁸Pb. There is still a fourth isotope, ²⁰⁴Pb, which makes up the remaining 1.5% and which is not the product of any radioactive series at all.

The isotopes always have atomic weights that are close to, but not quite, whole numbers. Any atomic weight of an element that departs appreciably from an integer does so only because it is an average of different isotopes. For instance, the atomic weight of chlorine (chemical symbol Cl) is 35.5, but this is because it is made up of a mixture of 2 isotopes. About one quarter of chlorine’s atoms are ³⁷Cl and about three-quarters are ³⁵Cl.

To avoid confusion, the average mass of the isotopes that make up a particular element is still called the atomic weight of that element. The integer closest to the mass of the individual isotope is spoken of as the “mass number” of that isotope. Thus, chlorine is made up of isotopes with mass numbers 35 and 37, but the atomic weight of chlorine as it is found in nature is 35.5 (or, to be more accurate, 35.453).

In the same way, ordinary lead is made up of isotopes with mass numbers 204, 206, 207, and 208, and its atomic weight is 207.19; neon is made up of isotopes with mass numbers 20, 21, and 22, and its atomic weight is 20.183, and so on.

If the atomic weight of some element happens to be very close to a whole number to begin with, it may consist of a single kind of atom. For instance, the gas fluorine (chemical symbol F) has an atomic weight of nearly 19, while that of the metal sodium (chemical symbol Na) is nearly 23. As it turns out, all the atoms of fluorine are of the single variety ¹⁹F, while all the atoms of sodium are ²³Na.

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Sometimes the atomic weight of an element, as it occurs in nature, is nearly a whole number and yet it is made up of more than 1 isotope. In that case, one of the isotopes makes up very nearly all of it, while the others are present in such minor quantities that the average is hardly affected.

Helium, for instance (atomic symbol He) has an atomic weight of just about 4 and, indeed, almost all the atoms making it up are ⁴He. However, 0.0001% of the atoms, or one out of a million, are ³He. Again, 99.6% of all the nitrogen atoms (atomic symbol N) are ¹⁴N, but 0.4% are ¹⁵N. Then, 98.9% of all carbon atoms (atomic symbol C) are ¹²C, but 1.1% are ¹³C. It is not surprising that the atomic weights of nitrogen and carbon are just about 14 and 12, respectively.

Even hydrogen does not escape. Its atomic weight is just about 1 and most of its atoms are ¹H. The American chemist Harold Clayton Urey (1893- ) detected the existence of a 45more massive isotope, ²H. This isotope has almost twice the mass of the lighter one. No other isotopes of a particular atom differ in mass by so large a factor. For that reason ²H and ¹H differ in ordinary chemical properties more than isotopes usually do and Urey therefore gave ²H the special name of “deuterium” from a Greek word meaning “second”.

In 1929 the American chemist William Francis Giauque (1895- ) found that oxygen was composed of more than 1 isotope. Its atomic weight had been set arbitrarily at 16.0000 so it was a relief that 99.76% of its atoms were ¹⁶O. However, 0.20% were ¹⁸O, and 0.04% were ¹⁷O.

As you see, ¹⁶O must have a mass number of slightly less than 16.0000 and it must be the more massive isotopes ¹⁷O and ¹⁸O that pull the average up to 16.0000. Disregarding this, chemists clung to a standard atomic weight of 16.000 for oxygen as it appeared in nature, preferring not to concern themselves with the separate isotopes.

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Physicists, however, felt uneasy at using an average as standard for they were more interested in working with individual isotopes. They preferred to set ¹⁶O at 16.0000 so that the average atomic weight of oxygen was 16.0044 and all other atomic weights rose in proportion. Atomic weights determined by this system were “physical atomic weights”.

Finally, in 1961, a compromise was struck. Chemists and physicists alike decided to consider the atomic weight of ¹²C as exactly 12 and to use that as a standard. By this system, the atomic weight of oxygen became 15.9994, which is only very slightly less than 16.

The radioactive elements did not escape this new view either. The atomic weight of uranium (chemical symbol U) is just about 238 and, indeed, most of its atoms are ²³⁸U. In 1935, however, the Canadian-American physicist, Arthur Jeffrey Dempster (1886-1950), found that 0.7% of its atoms were a lighter isotope, ²³⁵U.

These differed considerably in radioactive properties. The common uranium isotope, ²³⁸U, had a half-life of 4500 million years, while ²³⁵U had a half-life of only 700 million years. Furthermore ²³⁵U broke down in three stages to actinium. It was ²³⁵U, not actinium itself, that was the beginning of the actinium radioactive series.

As for thorium (atomic symbol Th) with an atomic weight of 232, it did indeed turn out that in the naturally occurring element virtually all the atoms were ²³²Th.