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The technique involves the expansion of a gas or mixture of gases through a Laval nozzle from a high pressure reservoir into a vacuum chamber. As it expands, the nozzle collimates the gas into a uniform supersonic beam which is essentially collision free and which has a temperature which, in the centre of mass frame, can be significantly below that of the reservoir gas. Each nozzle produces a characteristic temperature; in this way any temperature between room temperature and about 10K can routinely be achieved. There are relatively few CRESU apparatuses in existence for the simple reason that the gas throughput and pumping requirements are huge - which of course means that they are expensive to run. Two of the leading centres have been the University of Rennes (France) and the University of Birmingham (UK). A more recent development has been a pulsed version of the CRESU, which requires far less gas and therefore smaller pumps. One might well ask why we should use such a complex method for producing low temperature gases when they could be produced much more easily using liquid helium. The answer is simple: most species have a negligible vapour pressure at such low temperatures and this means that they would quickly condense on the sides of the apparatus. Essentially, the CRESU technique provides a "wall-less test tube" which allows the kinetics of gas phase reactions to be investigated at much lower temperatures than would be otherwise possible.
Chemical kinetics experiments can then be carried out in a "pump-probe" fashion using a laser to initiate the reaction (for example by preparing one of the reagents by photolysis of a precursor), followed by observation of a product (for example by laser induced fluorescence) after a known time delay. The time delay can also be varied (if one of the products fluoresces) by positioning a light detector such as a photomultiplier a known distance from the position at which the reaction begins. If the velocity of the gas flow is know it is therefore easy to calculate the reaction time. In this way it is similar to a flow tube experiment.
Reactions which studied by the CRESU technique are typically those which have no significant activation energy barrier. In the case of neutral-neutral reactions (i.e. not involving any charged species, ions), these type of barrier-free reactions usually involve free radical species such as molecular oxygen (O2), the cyanide radical (CN) or the hydroxyl radical (OH). The energetic driving force for these reactions is typically an attractive long range intermolecular potential.
CRESU experiments have been used to show deviations from Arrhenius kinetics at low temperatures: as the temperature is reduced, the rate constant actually increases. The can explain why chemistry is so prevalent in the interstellar medium, where many different polyatomic species have been detected (by radio astronomy), but where temperatures are so low that conventional wisdom might suggest that chemical reactions would not occur.
|This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "CRESU_experiment". A list of authors is available in Wikipedia.|