Periodic table trends

The Periodic Table of the Chemical Elements is an ultimate and fundamental of nature or merely a tool for creating useful patterns in chemistry. Discuss.

It could be a critical essay title from an undergraduate course in the philosophy of chemistry but it isn’t, it’s a real life periodic debate that rages on year after year among chemists who hope to find an ultimate form for the Periodic Table and those who suggest that any form will do as long as it is useful iin education and research. I recently published a summary of the state of the art regarding such forms and the stance of those who see them as nothing more than aesthetic variations on the theme and those who regard them as taking us a step closer to such an ultimate form for the Table. You can read the periodic debate over how the Table is complete, but not finished in my June Research Highlight column on Chemistry Views. A more in-depth version of the article in which UCLA’s Eric Scerri offers up a radically different PT and in which Martyn Poliakoff of Periodic Table of Videos fame rebuts the notion that such efforts are taking us closer to the ideal Periodic Table.

The aesthetics and ethics of elemental periodicity

It seems that the Periodic Table is in trouble. Well, not trouble exactly but aside from revisions to the atomic weights announced recently and the official adding to the Table of two “new” elements, 114 and 116, the poetically named and fleeting ununquadium and ununhexium, there is a debate bubbling like a reflux condenser about what precisely the Periodic Table is and what form it should take.

For decades chemistry educators and laboratory technicians have sat back and watched the corners of their good-old Periodic Table wall charts curl, each element in its box, trapped forever, with no alchemical chance to move. But that might soon change. Of course, there have been lots of attempts to rebuild the periodic table over the past 150 years. For instance, there are those, such as museum exhibit designer Roy Alexander, who suggests that in the twenty-first century, the 2D is not to be, and that it is high time that chemists made the switch to a 3D format for the Periodic Table. After all, if it’s good enough for Hollywood and Wimbledon, it should be good enough for chemists.

Spiralling into control

There are those who have attempted to create intriguing spiral Periodic Tables, circular efforts and even fractal charts. One Table dating back to the 1930s considers the sub-atomic particle, the neutron, as itself a element and lists the noble gases twice. In the 1920s Charles Janet built a stepped Periodic Table, which was much wider than the standard PT and would inevitably have been less than convenient for textbook publishers and wall chart printers alike.

Others suggest that subtle rearrangements of various elements would make the Periodic Table more intuitive and circumvent various discrepancies that have arisen as nuclear understanding evolved. Chemical philosopher Eric Scerri of the University of California Los Angeles is among that number. He is devising an alternative approach to elemental organization, which he suggests takes us closer to an ultimate version of the PT. Scerri’s argument for change is based on the fact that Periodic Table arose from the discovery of triads of atomic weights, but he thinks chemists would be better served if they were to recognize the fundamental importance of triads of atomic number instead. His new Periodic Table takes this phenomenon into account.

Scerri stuff indeed

The revision of the Periodic Table to this Scerri form is perhaps especially pertinent given that atomic mass varies according to isotope ratio (neutron count, in other words), whereas atomic number (proton count) is fixed for each element. In it, listings of electron shells follow an ordered pattern, so that the halogens form the first column on the left, topped by hydrogen, the noble gases are the second column, topped by helium. The alkali metals and the alkaline earth metals follow, then the block of transition metals. The semi-metals and the non-metals then form the final four columns. As if this restructuring of the groups were not controversial enough, it is the logical placements of hydrogen and helium that stirs chemical emotions. In relocating H and He, Scerri recreates the atomic number triads of He-Ne-Ar and H-F-Cl; these are not visible in the conventional PT.

However, not everyone is convinced by helium’s placement. Among them is American chemist Henry Bent, known for “Bent’s Rule” of molecular orbitals used by organic chemists and variously written as: “atomic ‘s’ character tends to concentrate in orbitals that are directed toward electropositive groups and atomic p character tends to concentrate in orbitals that are directed toward electronegative groups.” Bent would prefer to see helium atop beryllium in the otherwise “normal” PT layout. He argues that although helium seems to fit perfectly at the top of the noble gases its presence there breaks several of the rules. For instance, a Periodic Group’s first member is never the member of a primary (vertical) triad. This rule holds for 30 of the 32 Groups when He is above Ne. The two exceptions are He-Ne-Ar and Be-Mg-Ca. Move He above Be and the rule now holds for all 32 Groups.

Getting the He-Be-gee-bees

The He-Be debate is something of an aside to the philosophical debate that Scerri has unleashed by being quite so adamant that all the various Periodic Table arrangements are moving towards an ultimate version. He doesn’t wish to imply that his version is the essential, final version of which he speaks, but it is perhaps a step closer than the conventional PT we all know and love. “My belief is that there is one true and objective periodic classification even if we have not yet arrived at it,” he says.

Others, such as Philip Stewart, a longstanding fan of the spiral Periodic Table painted by artist Edgar Longman for the Science Exhibition of the 1951 Festival of Britain, based on chemist John Drury Clark’s 1933 original, is not convinced. Stewart argues that to search for “The Ideal Periodic Representation” is to take leave of the messy world of everyday bodies and drift off into Platonic mysticism. Software developer Melinda Green who developed a fractal Periodic Table for educational use agrees and says that an ultimate PT does not exist. Our perspective inevitably distorts reality, she says, any arrangement is purely subjective. “Neither the periodicity nor any classification is intrinsic to nature,” explains Green. “Periods of what? Where do these classes come from? They come from us to suit our particular purposes,” she says.

Atomic number is perhaps the only intrinsic property of the elements, as suggested by Scerri too, but, adds Green, this is only fundamental by our subjective definition of the term “element” rather than it representing something ultimate about the universe as Scerri’s reasoning would suggest. “I don’t believe that there are any ways to describe anything about the universe without a relative position from which to describe,” adds Green. “Every description requires a describer. Subjectivity is not just an annoyance, it is the source of all meaning.”

Chemistry’s rich pageant

Stewart suggests that we should think of the rich variety of images that have been proposed in the last 150 years as “something more like an art exhibition than a competition to achieve perfection. So, is the elemental menagerie, nothing more than an art gallery? Martyn Poliakoff thinks so. Poliakoff is a professor of chemistry at the University of Nottingham, England, who works on supercritical fluids but has gained fame recently for his involvement in a science engagement project known as the Periodic Table of Videos that has gone “viral” on the internet. Poliakoff takes an entirely pragmatic approach to the PT. “I regard the PT as a tool like a hammer and, just like other tools, you have different forms for different purposes (e.g. a claw-hammer and a mallet). There just isn’t a “right” and “wrong” form. The different forms highlight different aspects,” he says. He suggests that the different forms can be useful, however. “I think that these weird forms of the PT often serve a purpose by highlighting some aspect of the elements that one might not otherwise have noticed,” he says.

However, Scerri is convinced that there is something more fundamental to the ultimate PT. “It concerns me that scientists can express ‘relativistic’ [aesthetic] views on something as important as the Periodic Table,” he says. “It is, after all, the most basic, profound and deep classification that has ever been discovered.” The way we perceive the elements and their relationships with each other is fundamental to understanding matter, Scerri believes. The elements are natural entities, they are not building blocks we have constructed for our convenience. The patterns they obey follow objective rules, laws if you will, that are not decided by us and so do not succumb to the whim of the designers of novel Periodic Tables, stepped, 2D, 3D, spiral, fractal or otherwise.

Practical conclusion

Ever the pragmatist, Poliakoff points out a fact of periodic life that may be inescapable in efforts to raise the Periodic Table to some higher position in science. “In the end, I think that one should remember that Mendeleev devised the Periodict Table for a textbook to help rationalize the mass of facts in inorganic chemistry and to make them easier to teach,” he says. “For me, the PT remains just that, a tool to help reduce the complexity, not a metaphysical truth that has a correct form, as yet to be discovered.”

  • Scerri stuff indeed (sciencebase.com)
  • Two new elements officially added to periodic table (theglobeandmail.com)

Metallic liquid crystals

A new class of materials formed by combining liquid crystals and metal clusters glow intensely red in the infra-red region of the electromagnetic spectrum when irradiated over a broad range of wavelengths. The materials, dubbed clustomesogens, could be used in analytical instrumentation and potentially in display technologies.

Liquid crystals are well known in display technologies from digital watches to flat panel televisions. As their name suggests, they are at once liquid and can flow, but their molecules can also be oriented into something akin to a crystal state, usually under the influence of an electric field.

A second class of materials of interest to the optoelectronics field is metal clusters. Clusters are aggregates of just a few atoms, and so their properties are not those of individual atoms nor of the bulk metal, but somewhere in between. Indeed, metal clusters show some rather unusual electronic, magnetic, and optical properties because of the presence of the particular types of bonds that form between metals when just a few are present.

Now, Yann Molard, of the University of Rennes, in France, and colleagues there and at the University of Bucharest have united the two classes in clustomesogens to create metal clusters that exist in a liquid-crystalline phase.

Liquid crystals containing bonds between metal atoms are rare and usually limited to compounds in which just two metal atoms are connected in each unit. Molard and colleagues have produced liquid crystals that contains octahedral clusters made of six molybdenum atoms. Eight bromide ions sit on the eight surfaces of the octahedron, six fluorides and an aromatic organic group, or ligand, is at each vertex of the octahedron. These aromatic ligands each have three long hydrocarbon chains also ending in a pair of aromatic rings.

Yann Molard
Yann Molard

Simple warming these materials initiates a process of self-organization in which the clusters stretch out to form long, narrow units arranged in what is known as a lamellar, plate-like, structure. The flat rings at the ends of the ligands of neighbouring layers are interleaved and the structure has liquid-crystalline properties.

“The association of mesomorphism with the peculiar properties of metallic clusters should lead to clustomesogens that offer great potential in the design of new electricity-to-light energy conversion systems, optically based sensors, and displays,” the team says.

Links

Angew Chem Int Edn, 2010, 49, 3351-3355
Yann Molard homepage

Cool for cats

Chemists in the US have demonstrated a definitive link between the size of catalyst particles on a solid surface, their electronic properties and their ability to accelerate a chemical reaction. The study could help improve the design of yet more-efficient catalysts to reduce energy requirements for countless industrial processes and cut greenhouse gas emissions.

Ideally, catalysts are substances that speed chemical reactions without themselves being consumed in the reaction. In reality, they are never 100 percent efficient, can be degraded by repeated reaction cycles, and often become poisoned by by-products. Nevertheless, they are at the heart of thousands of chemical reactions used to make everything from pharmaceuticals to plastics.

“One of the big uncertainties in catalysis is that no one really understands what size particles of the catalyst actually make a chemical reaction happen,” says Scott Anderson of the University of Utah. “If we could understand what factors control activity in catalysts, then we could make better and less expensive catalysts.”

Catalysts are commonly made from rare metals including, gold, rhodium, palladium, and platinum, and there is typically a range of catalyst particle sizes present. In almost all cases, the size of the most active particles is unknown. In gold catalysts, which have been intensively studied recently, it has been shown that the bulk of the metal in a catalyst powder exists in the form of particles that are too big to do any catalysis, and only a small fraction of the metal is active.

“If you could make a catalyst with only the right size particles, you could save 90 percent of the cost or more,” asserts Anderson. He also points out that switching to cheaper and more common metals, such as zinc, nickel, and copper, and “tuning” their properties would also let chemists reduce costs significantly. The process of tuning such base metals would involve reducing the particle size until it reaches a catalytic optimum, which is the focus of the Utah team’s work.

Previous work showed how to alter electronic and chemical properties of a catalyst in a gas, but things are different once the particles are mounted on a metal oxide surface for real-life industrial processes.

Anderson and Kaden working to accelerate chemical reactions efficiently (Credit: William Kunkel, University of Utah)
Anderson and Kaden working to accelerate chemical reactions efficiently (Credit: William Kunkel, University of Utah)

In the new study, Anderson and his students took a step toward tuning catalysts to have desired properties. In work with Bill Kaden and William Kunkel, and Tianpin Wu, the team has demonstrated, for the first time, that the size of palladium metal catalyst “nanoparticles” deposited on a titanium dioxide surface affects not only the catalyst’s level of activity in converting carbon monoxide to carbon dioxide, but also the particles’ electronic properties.

As the size of a catalyst metal particle is reduced to the nanoscale, its properties initially remain the same as bulk metal. However, when the particles are just 10 nanometres across (containing 10,000 atoms or so) the movements of electrons in the metal become confined, so boosting their energy.

When there are fewer than about 100 atoms in catalyst particles, the size variations also result in fluctuations in the electronic structure of the catalyst atoms. Those fluctuations strongly affect the particles’ ability to act as a catalyst, Anderson says.

The study not only showed how catalytic activity varies with catalyst particle size, “but we have been able to correlate that size dependence with observed electronic differences in the catalyst particles,” Kaden adds. “People had speculated this should be happening, but no one has ever seen it.”

Links:

Science, 2009, in press
Scott L. Anderson homepage