MIT, University Minnesota Researchers Discovered 37th Type Chemical Reaction

Scientists explain new type of chemical reaction

9:57 AM, 5th September 2013
Research From MIT and University of Minnesota
Diagram illustrates the newly-discovered reaction that transforms molecules of ketohydroperoxide into acids and carbonyl molecules, after going through intermediate stages.

CAMBRIDGE, US: Previous studies have shown the existence of 36 basic types of chemical reactions. Researchers at MIT and the University of Minnesota have added a 37th type of reaction 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 research was conducted by William Green, Chemical Engineering Professor, MIT and Amrit Jalan, Graduate Student, MIT and six other researchers.

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.

“There were fundamental things about the way even simple hydrocarbons react with oxygen that we didn’t understand,” said Green. 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.

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 said 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, added Green.

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, said Green. He pointed 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,” added Green.

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

“A particularly nice aspect of this work is to then consider how this finding might be applicable to other systems. In a broader context, this combined effort by two very prominent research groups illustrates the power and potential for electronic structure calculations in quantitatively important problems in chemical kinetics,” said Anthony Dean, dean of the College of Applied Science and Engineering, Colorado School of Mines, who was not involved in this work.

“As a result of this clear exposition and the high level of theory that was applied, I believe this work will be widely accepted immediately. I certainly am already convinced by their conclusions,” said Stephen Klippenstein, Senior Scientist, Argonne National Laboratory in Illinois.

 

© Massachusetts Institute of Technology News

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