Forum for Science, Industry and Business

Sponsored by:     3M 
Search our Site:

 

Researchers Measure Reaction Rates of Second Key Atmospheric Component

12.04.2013
Work on Criegee Intermediate Published in Science Magazine

Researchers at Sandia National Laboratories’ Combustion Research Facility, the University of Manchester, Bristol University, University of Southampton and Hong Kong Polytechnic have successfully measured reaction rates of a second Criegee intermediate, CH3CHOO, and proven that the reactivity of the atmospheric chemical depends strongly on which way the molecule is twisted.

The measurements will provide further insight into hydrocarbon combustion and atmospheric chemistry. A paper describing the research findings titled “Direct Measurements of Conformer-Dependent Reactivity of the Criegee Intermediate CH3CHOO” is featured in the April 12 edition of Science magazine.

Criegee intermediates — carbonyl oxides — are considered to be pivotal atmospheric reactants, but only indirect knowledge of their reaction kinetics had previously been available. Last year, Sandia and its UK-based partners reported, for the first time, direct measurements of reactions of the smallest gas-phase Criegee intermediate using photoionization mass spectrometry. That research was featured in the January 13, 2012, edition of Science. A short video featuring two Sandia researchers describing the work can be seen here.

New findings include confirmed fast reactions, first-time measurements with water

Sandia combustion chemist Craig Taatjes, the lead author on the Science papers, said there are several significant aspects about the new research findings.

In particular, the measurements show that the reaction rate depends dramatically on whether the CH3CHOO is bent, with the CH3– and –OO ends pointing toward the same side, a conformation called “syn–” or more straightened, with the CH3– and –OO ends pointing away from each other, called “anti–”.

“Observing conformer-dependent reactivity represents the first direct experimental test of theoretical predictions,” said Taatjes. “The work will be of tremendous importance in validating the theoretical methods that are needed to accurately predict the kinetics for reactions of Criegee intermediates that still cannot be measured directly.”

In fact, said Taatjes, the latest results supply one of the most critical targets for such validation. Because of the large concentration of water in Earth’s atmosphere, Criegee concentrations — and, hence, the tropospheric implications of all Criegee intermediate reactions — depend on knowing the rate constant for reaction with water.

Although the reactions for most Criegee intermediates, including the syn- conformer of CH3CHOO, with water may simply be too slow to be measured by the research team’s methods, anti-CH3CHOO has been predicted to have a vastly enhanced reactivity with water. Taatjes and his colleagues confirmed this prediction and made the first experimental determination of the reaction rate of a Criegee intermediate with water. “A Criegee intermediate’s reaction with water determines what the concentration of these intermediates in the atmosphere is going to be. This is a significant benchmark,” he said.

Taatjes said one of the questions remaining after the first direct measurement of Criegee reactions was whether the remarkably fast reaction of CH2OO with SO2 was representative of other Criegee intermediates.

“This measurement of a second intermediate — which we found to react just about as fast with sulfur dioxide as the intermediate we measured last year — supports the notion that the reactions of all Criegee intermediates with SO2 will occur easily,” said Taatjes “It also confirms that Criegee intermediate reactions are likely to make a contribution to sulfate and nitrate chemistry in the troposphere.” This increase in reactivity, he said, provides additional evidence that Criegee intermediates will play a significant role in the oxidation of sulfur dioxide in the atmosphere.

Unraveling the mysteries, complexities of Criegee intermediates

Hydrocarbons that are emitted into Earth’s troposphere, either naturally or by humans, are removed by many reactive atmospheric species. For unsaturated hydrocarbons — molecules with at least one C=C double bond — a prominent removal mechanism is reaction with ozone, called ozonolysis. It is accepted that ozonolysis produces other reactive species, including carbonyl oxides, which are known as Criegee intermediates. Rudolf Criegee, a German chemist, first proposed the mechanism of ozonolysis in the 1950s.

Because so much ozonolysis happens in the atmosphere, the reactions of Criegee intermediates are thought to be very important in a wide range of tropospheric processes like secondary organic aerosol formation and nighttime production of highly reactive OH radicals. As a result, the chemistry of these reactive Criegee intermediates has been the subject of intense investigation for decades, but without any direct measurement of their reaction rates until last year’s published work by Sandia and its collaborators.

The research was funded by the U.S. Department of Energy's Office of Science and conducted using the Advanced Light Source, a scientific user facility also supported by the DOE Office of Science.

Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin company, for the U.S. Department of Energy’s National Nuclear Security Administration. With main facilities in Albuquerque, N.M., and Livermore, Calif., Sandia has major R&D responsibilities in national security, energy and environmental technologies and economic competitiveness.

Sandia news media contact: Mike Janes, mejanes@sandia.gov, (925) 294-2447

Mike Janes | Newswise
Further information:
http://www.sandia.gov

More articles from Ecology, The Environment and Conservation:

nachricht Listening in: Acoustic monitoring devices detect illegal hunting and logging
14.12.2017 | Gesellschaft für Ökologie e.V.

nachricht How fires are changing the tundra’s face
12.12.2017 | Gesellschaft für Ökologie e.V.

All articles from Ecology, The Environment and Conservation >>>

The most recent press releases about innovation >>>

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

Im Focus: Error-free into the Quantum Computer Age

A study carried out by an international team of researchers and published in the journal Physical Review X shows that ion-trap technologies available today are suitable for building large-scale quantum computers. The scientists introduce trapped-ion quantum error correction protocols that detect and correct processing errors.

In order to reach their full potential, today’s quantum computer prototypes have to meet specific criteria: First, they have to be made bigger, which means...

Im Focus: Search for planets with Carmenes successful

German and Spanish researchers plan, build and use modern spectrograph

Since 2016, German and Spanish researchers, among them scientists from the University of Göttingen, have been hunting for exoplanets with the “Carmenes”...

Im Focus: First-of-its-kind chemical oscillator offers new level of molecular control

DNA molecules that follow specific instructions could offer more precise molecular control of synthetic chemical systems, a discovery that opens the door for engineers to create molecular machines with new and complex behaviors.

Researchers have created chemical amplifiers and a chemical oscillator using a systematic method that has the potential to embed sophisticated circuit...

Im Focus: Long-lived storage of a photonic qubit for worldwide teleportation

MPQ scientists achieve long storage times for photonic quantum bits which break the lower bound for direct teleportation in a global quantum network.

Concerning the development of quantum memories for the realization of global quantum networks, scientists of the Quantum Dynamics Division led by Professor...

Im Focus: Electromagnetic water cloak eliminates drag and wake

Detailed calculations show water cloaks are feasible with today's technology

Researchers have developed a water cloaking concept based on electromagnetic forces that could eliminate an object's wake, greatly reducing its drag while...

All Focus news of the innovation-report >>>

Anzeige

Anzeige

Event News

See, understand and experience the work of the future

11.12.2017 | Event News

Innovative strategies to tackle parasitic worms

08.12.2017 | Event News

AKL’18: The opportunities and challenges of digitalization in the laser industry

07.12.2017 | Event News

 
Latest News

Single-photon detector can count to 4

18.12.2017 | Information Technology

Quantum memory with record-breaking capacity based on laser-cooled atoms

18.12.2017 | Physics and Astronomy

How much soil goes down the drain -- New data on soil lost due to water

18.12.2017 | Agricultural and Forestry Science

VideoLinks
B2B-VideoLinks
More VideoLinks >>>