Forum for Science, Industry and Business

Sponsored by:     3M 
Search our Site:

 

New low-temperature chemical reaction explained

05.09.2013
Unusual reaction, never fully understood, is important to fuel combustion, atmospheric chemistry and biochemistry

In all the centuries that humans have studied chemical reactions, just 36 basic types of reactions have been found. Now, thanks to the work of researchers at MIT and the University of Minnesota, a 37th type of reaction can be added to the list.

The newly explained reaction — whose basic outlines had been known for three decades, but whose workings had never been understood in detail — is an important part of atmospheric reactions that lead to the formation of climate-affecting aerosols; biochemical reactions that may be important for human physiology; and combustion reactions in engines.

The new analysis is explained in a paper by MIT graduate student Amrit Jalan, chemical engineering professor William Green, and six other researchers, published in the Journal of the American Chemical Society.

The reaction's details sound esoteric: a low-temperature oxidation that results in the decomposition of complex organic molecules known as gamma-ketohydroperoxides. When he first described the reaction in the scientific literature 30 years ago, Stefan Korcek of the Ford Motor Company proposed a hypothesis for how the reaction might take place. The new work shows that Korcek had the right concept, although some details differ from his predictions.

The original discovery was the result of analyzing how engine oils break down through oxidation — part of an attempt to produce oils that would last longer. That's important, Green points out, since waste oil is among the largest hazardous waste streams in the United States.

In analyzing the problem, Korcek realized that "there were fundamental things about the way even simple hydrocarbons react with oxygen that we didn't understand," Green says. By examining the products of the reaction, which included carboxylic acids and ketones, Korcek outlined an unusually complex multipart reaction. But for the next three decades, nobody found a way to verify whether the reaction or the steps he outlined could work.

Jalan says that the MIT researchers' analysis came about almost by accident. "I was looking at that paper for a different study," he says, "and I came across [Korcek's] work, which hadn't been verified either theoretically or experimentally. … [We] decided to see if we could explain his observations by throwing quantum mechanical tools at the problem."

In collaboration with the Minnesota researchers — including Donald Truhlar, a co-author of the new paper and a leading expert in such calculations — Jalan and Green were able to demonstrate exactly why the reaction works as it does. But they also found that part of the process must differ slightly from Korcek's original hypothesis.

Green says that understanding how this "very important reaction" works could be significant in several fields. The researchers' initial impetus was, in part, a colleague's exploration of biofuel combustion. The new understanding of the degradation that can take place as different fuels oxidize — sometimes producing toxic or corrosive byproducts — could help narrow the choice of fuel types to pursue, he says.

The process is also related to oxidations that take place in the body, contributing to the tissue damage and aging that antioxidant vitamins seek to combat, Green says.

Green points out that because this is an entirely new type of reaction, it opens the door to research on other variations. "Once you discover a new type of reaction, there must be many similar ones," he says.

"It's very odd to have so many reactions at once in such a small molecule," Green adds. "Now that we know that can happen, we're searching for other cases."

The research was supported in part by the U.S. Department of Energy, and used computing facilities at the Pacific Northwest National Laboratory and the Minnesota Supercomputing Institute.

Written by David Chandler, MIT News Office

Andrew Carleen | EurekAlert!
Further information:
http://www.mit.edu

More articles from Life Sciences:

nachricht Symbiotic bacteria: from hitchhiker to beetle bodyguard
28.04.2017 | Johannes Gutenberg-Universität Mainz

nachricht Nose2Brain – Better Therapy for Multiple Sclerosis
28.04.2017 | Fraunhofer-Institut für Grenzflächen- und Bioverfahrenstechnik IGB

All articles from Life Sciences >>>

The most recent press releases about innovation >>>

Die letzten 5 Focus-News des innovations-reports im Überblick:

Im Focus: Making lightweight construction suitable for series production

More and more automobile companies are focusing on body parts made of carbon fiber reinforced plastics (CFRP). However, manufacturing and repair costs must be further reduced in order to make CFRP more economical in use. Together with the Volkswagen AG and five other partners in the project HolQueSt 3D, the Laser Zentrum Hannover e.V. (LZH) has developed laser processes for the automatic trimming, drilling and repair of three-dimensional components.

Automated manufacturing processes are the basis for ultimately establishing the series production of CFRP components. In the project HolQueSt 3D, the LZH has...

Im Focus: Wonder material? Novel nanotube structure strengthens thin films for flexible electronics

Reflecting the structure of composites found in nature and the ancient world, researchers at the University of Illinois at Urbana-Champaign have synthesized thin carbon nanotube (CNT) textiles that exhibit both high electrical conductivity and a level of toughness that is about fifty times higher than copper films, currently used in electronics.

"The structural robustness of thin metal films has significant importance for the reliable operation of smart skin and flexible electronics including...

Im Focus: Deep inside Galaxy M87

The nearby, giant radio galaxy M87 hosts a supermassive black hole (BH) and is well-known for its bright jet dominating the spectrum over ten orders of magnitude in frequency. Due to its proximity, jet prominence, and the large black hole mass, M87 is the best laboratory for investigating the formation, acceleration, and collimation of relativistic jets. A research team led by Silke Britzen from the Max Planck Institute for Radio Astronomy in Bonn, Germany, has found strong indication for turbulent processes connecting the accretion disk and the jet of that galaxy providing insights into the longstanding problem of the origin of astrophysical jets.

Supermassive black holes form some of the most enigmatic phenomena in astrophysics. Their enormous energy output is supposed to be generated by the...

Im Focus: A Quantum Low Pass for Photons

Physicists in Garching observe novel quantum effect that limits the number of emitted photons.

The probability to find a certain number of photons inside a laser pulse usually corresponds to a classical distribution of independent events, the so-called...

Im Focus: Microprocessors based on a layer of just three atoms

Microprocessors based on atomically thin materials hold the promise of the evolution of traditional processors as well as new applications in the field of flexible electronics. Now, a TU Wien research team led by Thomas Müller has made a breakthrough in this field as part of an ongoing research project.

Two-dimensional materials, or 2D materials for short, are extremely versatile, although – or often more precisely because – they are made up of just one or a...

All Focus news of the innovation-report >>>

Anzeige

Anzeige

Event News

Fighting drug resistant tuberculosis – InfectoGnostics meets MYCO-NET² partners in Peru

28.04.2017 | Event News

Expert meeting “Health Business Connect” will connect international medical technology companies

20.04.2017 | Event News

Wenn der Computer das Gehirn austrickst

18.04.2017 | Event News

 
Latest News

Wireless power can drive tiny electronic devices in the GI tract

28.04.2017 | Medical Engineering

Ice cave in Transylvania yields window into region's past

28.04.2017 | Earth Sciences

Nose2Brain – Better Therapy for Multiple Sclerosis

28.04.2017 | Life Sciences

VideoLinks
B2B-VideoLinks
More VideoLinks >>>