Fluorine is the most reactive chemical element. That is why it is not found in nature in its elemental form, but only in compounds, such as fluorite – that was the accepted scientific doctrine so far. A special fluorite, the "fetid fluorite" or "antozonite", has been the subject of many discussions for nearly 200 years. This mineral emits an intensive odor when crushed. Now, for the first time, scientists from the Technische Universitaet Muenchen (TUM) and the Ludwig-Maximilians-University Munich (LMU) have successfully identified natural elemental fluorine in this fluorspar. They report their results in the international edition of the scientific journal Angewandte Chemie.
Being the most reactive of all chemical elements fluorine calls for extremely careful handling. It is so aggressive that glass laboratory instruments cannot resist it and even bricks burn when exposed to fluorine gas. Yet elemental fluorine has numerous industrial applications including corrosion prevention or fuel tank diffusion barriers and it is used for the production of sulphur hexafluoride, which serves as insulating material in high voltage switches.
Because of its extreme properties, until now chemists were convinced that fluorine cannot occur in nature in its elemental form, but only as a fluoride ion, for instance in minerals such as fluorite (CaF2), also known as fluorspar. A certain variety of it, the so-called "fetid fluorite" or "antozonite" from the "Maria" mine in Woelsendorf in the Upper Palatinate (Germany), has been an object of contention in science for some 200 years. When crushed, it emits an unpleasant, pungent smell.
A number of eminent chemists, among them Friedrich Woehler (1800-1882) and Justus von Liebig (1803-1873), proposed various substances to explain the odor. Over the years, scientists resorted to olfactory tests, chemical analyses and complex mass spectrometer studies – coming to very different conclusions. Next to elemental fluorine, substances like iodine, ozone, phosphorus compounds, arsenic, sulphur, selenium, chlorine, hypochlorous acid and hydrofluorocarbons were made responsible for the smell. Direct evidence that this fluorspar has inclusions of fluorine and that the gas does not form during crushing was lacking hitherto.
Now, finally, a scientific team led by Florian Kraus, head of the Fluorine Chemistry Work Group at the Department of Chemistry of the Technische Universitaet Muenchen, and by Joern Schmedt auf der Guenne, head of the Emmy-Noether Work Group for Solid State NMR at the Department of Chemistry of the Ludwig-Maximilians-University Munich, have succeeded in directly proving the presence of fluorine in "antozonite" beyond any doubt. Using 19F-NMR spectroscopy, they were able to identify the fluorine "in-situ", i.e. non-destructively in its natural environment, and thereby put an end to the long discussions about the cause for the odor of "stinking fluorspar".
"It is not surprising that chemists doubted the existence of elemental fluorine in fetid fluorite," explain the researchers. "The fact that elemental fluorine and calcium, which would normally react with each other at once, are found here side by side is indeed hard to believe." However, in the case of "antozonite" there are very special conditions: The elemental fluorine is generated through minute uranium inclusions in the mineral, which constantly emit ionizing radiation and thus split the fluorite into calcium and elemental fluorine. The fluorine remains in minute inclusions, separated from the calcium by the non-reactive fluorite and thus retains its elemental form. The ionizing radiation also leads to the formation of calcium clusters, which give "antozonite" its dark color.
Technische Universitaet Muenchen: http://www.tum.de
This press release was posted to serve as a topic for discussion. Please comment below. We try our best to only post press releases that are associated with peer reviewed scientific literature. Critical discussions of the research are appreciated. If you need help finding a link to the original article, please contact us on twitter or via e-mail.
Structural colours are more visible and vivid than those that use pigments as many examples from the natural world demonstrate. But sometimes pure white is what is required
Dutch biologist Ingrid van der Meer often meets with disbelief when she talks about her work on dandelions and how it could secure the future of road transport.
Pretend for a minute that it’s 1875 and you’re a mining engineer whose job it is to figure out how much gold is in them thar hills. Get it wrong, and your company is going to waste a lot of time and money hunting for gold that’s not there—or worse yet, miss out on the mother lode
It can only switch from black to transparent and back again, but that's a start
What happens when you add folds to materials that are only a few atoms thick? Several scientists set out to find the answer — and discovered that these nano-wrinkles can be quite useful.
A battery tattoo powered by perspiration has been unveiled by chemists in California.
Huge earthquakes could be on the way to Chile, after the major quake in April this year failed to relieve seismic stresses that have built up for 150 years
The Swedish government is looking at building a nuclear reactor purely for research, although a decision will not be taken until after a general election in September, Swedish daily Dagens Industri reported.
A new movie turns the physicist into a romantic lead. But how will it handle the not-so-wonderful parts of his marriage? Truthaholics want to know.
Iranian mathematician Prof Maryam Mirzakhani becomes the first woman to win a Fields Medal at a ceremony in Seoul, South Korea.