thesis The straight dope on isotopes

A century ago this month, Frederick Soddy described and named isotopes in the pages of Nature. Brett F. Thornton and Shawn C. Burdette discuss how chemists have viewed and used isotopes since then — either as chemically identical or chemically distinct species as the need required and technology allowed.

Ernest Rutherford visited Stockholm in December 1908 to receive the Nobel Prize in Chemistry for his “investigations into

the disintegration of the elements, and FORGAN ROSS the chemistry of radioactive substances”1. Rutherford, a famously reluctant chemist, had hoped to be recognized for physics, but the discovery of radioactivity had deeply intertwined physics and chemistry more than at any time before or a!er. Investigations into radioactivity were accompanied by a multitude of reports describing new substances, tentatively called radio-elements, but in 1908 almost no one knew how to classify them. Mendeleev’s periodic table lacked enough gaps to accommodate all the new substances being found in samples of uranium and thorium, and some chemists even suggested that the periodic table was no longer a valid way to organize elements. A!er the Nobel ceremony, Rutherford met with two chemists from Uppsala University, Daniel Strömholm and a young The origin of ‘isotopes’. "eodor Svedberg. Strömholm and Svedberg were attempting to crystallize radio- elements for chemical characterization. later summarized the events surrounding spectrum10. "ough there was much debate, Using these methods, they hypothesized that the realization of isotopy, and included an Georg Hevesy and Friedrich Paneth’s the radio-elements radium, thorium X and apologetic acknowledgement of Strömholm’s critical experiments demonstrated that, actinium X were actually the same chemical and Svedberg’s research. Much of the early to their limits of accuracy, isotopes of lead element2 and, therefore, should be grouped work leading to the rationalization of behaved identically in an electrochemistry together on the periodic table. Today these isotopes was based on classical chemistry experiment11. "ey concluded that an species are recognized as 226Ra, 224Ra and techniques rather than physics-based element’s chemistry does not depend on 223Ra. Rutherford was highly sceptical methods, and isotopes were put on a solid which isotope it is. Although the early of the Swedes’ suggestion, and although footing just before Moseley’s X-ray studies experimenters were limited to studying discouraged, Strömholm and Svedberg $rmly established that each element has a only the relatively few isotopes that occur cautiously published their results2,3, which unique atomic number7. naturally on Earth, that limit soon lapsed. were largely ignored. Had they been bolder Soddy described isotopes as having Today there are about 3,000 known in making their claims, the pair might have “identical outsides but di%erent insides”8. We isotopes, and there could be 3,000–4,000 been credited with discovering isotopes, as now know that the ‘outsides’ — the electrons more12. Most isotopes are short-lived Svedberg would speculate much later. — cause all of an element’s isotopes to radioactive species. Elevating only stable "e evidence of chemically inseparable exhibit the same chemistry. "e protons and isotopes to element-like status would elements became more undeniable in May neutrons — the ‘insides’ — are spectators to be unwieldy and, for most chemistry, 1913 when J. J. "omson reported that neon the interactions of valence electrons. "is was unnecessary; however, subtle problems with seemed to be made of two gases with masses the original, but philosophically troubling, treating isotopes as chemically equivalent 20 and 22 (ref. 4). Nature then published understanding9. Some chemists believed entities soon emerged. When Harold Urey Frederick Soddy’s proposal on 4 December that isotopes must be chemically distinct. discovered 2H in 1931, deuterium was quickly 1913, which hypothesized that isotopes How could isotopes of a single element, shown to have di%erent chemical properties were “chemically identical elements of the made up of atoms that were di%erent, have from 1H. Although the hypothesis that same nuclear charge”5. "e name isotope, identical chemical properties? Earlier work isotopes were chemically identical was refuted from Greek words meaning ‘same place’, had had demonstrated that thorium and ionium, long ago, we still teach students that an been suggested to Soddy at a dinner party6. now known as two isotopes of thorium, element’s isotopes exhibit the same chemistry. Soddy’s Nobel Prize speech nine years seemed to have the same atomic emission How far do the real di%erences extend? "e

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although there is great variability. 13 Atmospheric CO2 has a δ C of about –8‰; in plants, δ13C is about –28‰. A positive δ13C means that the sample is 13C-enriched relative to the standard; a negative value means that the sample is depleted in 13C. Variations in these values can be used in elucidating food webs and which plants animals preferentially eat. Kinetic isotope e%ects have an

EMILIO SEGRE VISUAL ARCHIVES/AIP/SPL VISUAL EMILIO SEGRE impact, though o!en imperceptibly, on most chemical reactions. "e average mixture of an element’s isotopes varies slightly as matter moves through various systems on Earth. Most (74) of the $rst 92 elements have more than one isotope used in calculating their atomic weights, therefore these atomic masses are subject to variability. As far back as 1951, the IUPAC atomic weight revisions included a disclaimer about the atomic weight of sulfur because of variations found in natural materials. Advances in analytical and separation technologies have slowly led to the requirement for more footnotes in each Soddy’s work opened a fertile area of chemistry research. Pictured here, Glenn Seaborg, discoverer of succeeding revision. Six decades later, 12 many isotopes, stands in front of an isotope chart. elements have atomic weights that are given as ranges, not single values17,18. As elements become heavier, the KIE doubled mass of deuterium with respect to Alternatively, the kinetic isotope e%ect and relative di%erences in isotope masses protium represents the most extreme case: the (KIE) is based on mass-induced variations become smaller. In bromine, 79Br and 81Br di%erences are so pronounced that hydrogen inO chemistry. Chemical bonding interactions di%er in mass by less than 3%. Advances isotopes have special names. with a heavy isotope will usually occur more in experimental techniques have recently In 1946, Urey reviewed instances where slowly than with a lighter one. Molecules allowed bromine isotope fractionation to be isotopes of elements besides hydrogen with the lighter isotopes in reactive positions measured in atmospheric methyl bromide, behaved di%erently13. "is marked the become depleted relative to the analogous a naturally occurring and anthropogenically beginning of stable isotope studies, and a molecules with heavier isotopes at the same produced ozone-depleting gas. Knowing shi! to viewing isotopes as being chemically location. "e larger the mass di%erence, the the relative amounts of 79Br and 81Br in

distinct instead of identical. Although this larger the KIE. Reactions involving C–H CH3Br may help explain the uncertainties had been realized much earlier for deuterium, bonds are about 6–10 times faster than C–D in its sources and sinks in the environment. 13 81 the phenomenon was now recognized as bond reactions, whereas substituting C for Measuring δ Br of CH3Br means trapping being a possibility for the entire periodic 12C only slows reactions by about 1.04 times. and separating an 8 parts-per-trillion

table. Urey introduced the idea of using When carbonic anhydrase captures CO2, component of the atmosphere, and noting oxygen isotopes to deduce seawater paleo- 12C is preferentially incorporated into the variations in isotopic composition at a parts- 81 temperatures in 1948 (ref. 14). In natural and plant’s tissues. "e measurement of isotope per-thousand level. So far, δ Br of CH3Br arti$cial systems, a tiny preference for one fractionation, the ‘delta’ notation16 (δ13C), has been observed in the 0 to 1.75‰ range isotope over another in a frequently repeated is shown in equation (1). "e δ represents where 0‰ is the bromine composition reaction, such as carbon $xation by plants, the deviation of an isotope ratio in a sample of seawater19, providing a new tool for will lead to a di%erential isotope fractionation from the isotope ratio in a standard material. distinguishing amongst the many natural

in the reactants and products. "e zero value for δ is de$ned a standard sources and sinks of CH3Br. What is the nature of isotopes for chemists material. For carbon, the standard is Vienna "e KIE doesn’t explain all isotope e%ects today? Aside from the pioneers endeavouring Pee-Dee Belemnite, a synthetic standard however. Some reactions were observed to to create new isotopes (or elements), isotopes based on fossilized cephalopods, but other behave in exactly the opposite fashion of are tools for chemists. "ose isotopic tools element isotope standards are based on less what the KIE would predict, with heavier fall into two broad categories: (1) tools that obscure materials such as seawater. isotopes found to be more reactive. In the assume isotopes of an element are chemically 1970s, the magnetic isotope e%ect was 13 13 identical; and (2) tools that assume they C C elucidated. "is e%ect arises because of 12C − 12C are chemically distinct. Tools that assume 13 sample standard chemical reactions preferring to conserve δ C =×1,000 (1) 20 isotopes are chemically identical exploit 13 electron and nuclear spin . For instance, Mg isotopes as tracers. For example, elucidating C has three stable isotopes: 24Mg and 26Mg are 12 25 a biological process by observing the &ow of C standard spinless and non-magnetic, whereas Mg a spike of radioactive 14C through the system. has a nuclear spin and is magnetic, and can Such tracer uses were exploited very early, Typical δ values for reactions are a few to participate in electron–nuclear hyper$ne even before the word ‘isotope’ was coined15. tens of parts per thousand, or per mille (‰), coupling during reactions, potentially

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© 2013 Macmillan Publishers Limited. All rights reserved thesis introducing alternative reaction pathways. In For nearly a century, isotopes have Worcester, Massachusetts, USA. contrast, bromine’s two stable isotopes have been invisible to most chemists, but that e-mail: [email protected]; the same nuclear spin, so Br cannot exhibit is changing in small steps. Shi!ing isotope [email protected] magnetic isotope e%ects. compositions mean that the atomic weights are no longer universal constants24. References Students of chemistry o!en learn about 1. http://go.nature.com/7sOO55 Today there are about 3,000 2. Strömholm, D. & Svedberg. T. Z. Anorg. Chem. 63, 197–206 (1909). the simpler uses of isotopes based on 3. Strömholm, D. & Svedberg, T. Z. Anorg. Chem. 61, 338–346 (1909). known isotopes, and there chemical identicalness, though this is now 4. "omson, J. J. Proc. R. Soc. Lond. A 89, 1–20 (1913). changing25,26."e unique chemical nature of 5. Marshall, J. L. & Marshall, V. R. "e Hexagon 68–74 (2010). could be 3,000–4,000 more. 6. Soddy, F. W. Nature 92, 399–400 (1913). an element’s individual isotopes becomes 7. Moseley, H. G. J. Phil. Mag. 1024 (1913). more apparent when analysed at $ner scales, 8. http://go.nature.com/FpAXEz "e ability to measure isotope e%ects re&ecting a century of improvements in 9. Scerri, E. R. A Tale of Seven Elements (Oxford Univ. Press, 2013). 10. Russell, A. S. & Rossi, R. Proc. R. Soc. Lond. A 87, 478–484 (1912). has slowly spread to higher atomic analytical chemistry. 11. von Hevesy, G. & Paneth, F. Physik. Z. 15, 797–805 (1914). numbers. With more of the periodic table So what are isotopes to a modern 12. "oennessen, M. Rep. Prog. Phys. 76, 056301 (2013). now available, the applications of isotope chemist? What will they be in another 13. Urey, H. C. J. Chem. Soc. 562–581 (1947). 21 14. Urey, H. C. Science 108, 489–496 (1948). fractionation measurements will continue hundred years? Chemical curiosities, an 15. von Hevesy, G. & Paneth, F. Z. Anorg. Allg. Chem. to grow. Measuring more than one isotope area of active research, or a vital tool? "e 82, 323–328 (1913). system in a molecule, or multidimensional answer, ultimately, may depend on what type 16. Coplen, T. B. Rapid Commun. Mass Spectrom. 25, 2538–2560 (2011). ❐ 17. Wieser, M. E. & Coplen, T. B. Pure Appl. Chem. 83, 359–396 (2011). isotope analysis, can enable very detailed of chemist you are. 18. Wieser, M. E. et al. Pure Appl. Chem. 85, 1047–1078 (2013). sourcing of samples. Isotopes are the 19. Horst, A. et al. Tellus B 65, 21040 (2013). workhorses of geochemistry, tracers built into Brett F. "ornton is in the Department of 20. Buchachenko, A. L. J. Phys. Chem. B 117, 2231–2238 (2013). the fabric of Earth and the universe. Isotopes Geological Sciences (IGV) and Bolin Centre 21. Weiss, D. J. et al. Environ. Sci. Technol. 42, 655–664 (2008). 22. Ueno, Y. et al. Proc. Natl Acad. Sci. USA 106, 14784–14789 (2009). have proved invaluable at elucidating many for Climate Research, Stockholm University, 23. Webster, C. R. et al. Science 341, 260–263 (2013). aspects of the Earth’s history22. Farther a$eld, Stockholm, Sweden. 24. Coplen, T. B. & Holden, N. E. Chem. Int. 33, 10–15 (2011). isotopes are useful for understanding not Shawn C. Burdette is in the Department 25. Weiss, D. J., Harris, C., Maher, K. & Bullen, T. A. J. Chem. Educ. 90, 1014–1017 (2013). only the atmosphere of Mars, but the history of Chemistry and Biochemistry, 26. Iskenderian-Epps, W. S., Soltis, C. & O’Leary, D. J. J. Chem. Educ. of the atmosphere of Mars23. Worcester Polytechnic Institute, 90, 1044–1047 (2013).

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