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Le Chatelier's principle
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In chemistry, Le Chatelier's principle , also called Chatelier's principle or "The Equilibrium Law", can be used to predict the effect of a change in conditions on a chemical equilibrium. The principle is named after Henry Louis Le Chatelier and sometimes Karl Ferdinand Braun who discovered it independently. It can be summarized as: If a chemical system at equilibrium experiences a change in concentration, temperature, volume, or partial pressure, then the equilibrium shifts to counteract the imposed change and a new equilibrium is established. This principle has a variety of names, depending upon the discipline using it. See, for example, homeostasis. It is common to take Le Chatelier's principle to be a more general observation,[1] roughly stated: Any change in status quo prompts an opposing reaction in the responding system. In chemistry, the principle is used to manipulate the outcomes of reversible reactions, often to increase the yield of reactions. In pharmacology, the binding of ligands to the receptor may shift the equilibrium according to Le Chatelier's principle, thereby explaining the diverse phenomena of receptor activation and desensitization.[2] In economics, the principle has been generalized to help explain the price equilibrium of efficient economic systems. In simultaneous equilibrium systems, phenomena that are in apparent contradiction to Le Chatelier's principle can occur; these can be resolved by the theory of response reactions.
Contents
1 Status as a physical law 2 Chemistry 2.1 Effect of change in concentration 2.2 Effect of change in temperature 2.3 Effect of change in Pressure
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2.4 Effect of adding an inert gas 2.5 Effect of a catalyst 3 Applications in economics 4 See also 5 References 6 Bibliography 7 External links
Chemistry
Effect of change in concentration
Changing the concentration of an ingredient will shift the equilibrium to the side that would reduce that change in concentration. The chemical system will attempt to partially oppose the change affected to the original state of equilibrium. In turn, the rate of reaction, extent and yield of products will be altered corresponding to the impact on the system. This can be illustrated by the equilibrium of carbon monoxide and hydrogen gas, reacting to form methanol. CO + 2 H2 CH3OH
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Suppose we were to increase the concentration of CO in the system. Using Le Chatelier's principle, we can predict that the amount of methanol will increase, decreasing the total change in CO. If we are to add a species to the overall reaction, the reaction will favor the side opposing the addition of the species. Likewise, the subtraction of a species would cause the reaction to fill the "gap" and favor the side where the species was reduced. This observation is supported by the collision theory. As the concentration of CO is increased, the frequency of successful collisions of that reactant would increase also, allowing for an increase in forward reaction, and generation of the product. Even if a desired product is not thermodynamically favored, the end-product can be obtained if it is continuously removed from the solution.
H = -92 kJ mol-1
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N2 + 3 H2 2 NH3 H = -92kJ mol-1 4 volumes 2 volumes Note the number of moles of gas on the left-hand side and the number of moles of gas on the right-hand side. When the volume of the system is changed, the partial pressures of the gases change. If we were to decrease pressure by increasing volume, the equilibrium of the above reaction will shift to the left, because the reactant side has greater number of moles than does the product side. The system tries to counteract the decrease in partial pressure of gas molecules by shifting to the side that exerts greater pressure. Similarly, if we were to increase pressure by decreasing volume, the equilibrium shifts to the right, counteracting the pressure increase by shifting to the side with fewer moles of gas that exert less pressure. If the volume is increased because there are more moles of gas on the reactant side, this change is more significant in the denominator of the equilibrium constant expression, causing a shift in equilibrium.
Thus, an increase in system pressure due to decreasing volume causes the reaction to shift to the side with the fewer moles of gas.[4] A decrease in pressure due to increasing volume causes the reaction to shift to the side with more moles of gas. There is no effect on a reaction where the number of moles of
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Effect of a catalyst
A catalyst has no effect on equilibrium. It speeds up both forward and backward reactions equally. E.g.: N2 + 3 H2 2 NH3 Here Iron (Fe) and Molybdenum (Mo) are catalysts, but the two catalysts do not affect the state of equilibrium. Hence a catalyst has no effect on equilibrium state.
Applications in economics
In economics, a similar concept also named after Le Chatelier was introduced by U.S. economist Paul Samuelson in 1947. There the generalized Le Chatelier principle is for a maximum condition of economic equilibrium: Where all unknowns of a function are independently variable, auxiliary constraints"just-binding" in leaving initial
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equilibrium unchangedreduce the response to a parameter change. Thus, factordemand and commodity-supply elasticities are hypothesized to be lower in the short run than in the long run because of the fixed-cost constraint in the short run.[5]
See also
Homeostasis Common-ion effect Response reactions
References
1. ^ Gall, John (2002). The Systems Bible (3rd ed.). General Systemantics Press. "The System always kicks back" 2. ^ "The Biophysical Basis for the Graphical Representations" (http://www.biobalance.com/Graphics.htm) . Retrieved 2009-05-04. 3. ^ Kay, J. J. (February 2000) [1999]. "Application of the Second Law of Thermodynamics and Le Chatelier's Principle to the Developing Ecosystem". In Muller, F. Handbook of Ecosystem Theories and Management. Environmental & Ecological (Math) Modeling. CRC Press. ISBN 978-1-56670-253-9. "As systems are moved away from equilibrium, they will utilize all available avenues to counter the applied gradients... Le Chatelier's principle is an example of this equilibrium seeking principle." For full details, see: Ecosystems as Self-organizing Holarchic Open Systems: Narratives and the Second Law of Thermodynamics. p. 5. CiteSeerX: 10.1.1.11.856 (http://citeseerx.ist.psu.edu/viewdoc/summary?doi=10.1.1.11.856) . 4. ^ a b Atkins1993, p. 114 5. ^ Samuelson, Paul A (1983). Foundations of Economic Analysis. Harvard University Press. ISBN 0-674-31301-1.
Bibliography
Atkins, P.W. (1993). The Elements of Physical Chemistry (3rd ed.). Oxford University Press. Le Chatelier, H. and Boudouard O. (1898), "Limits of Flammability of Gaseous Mixtures", Bulletin de la Socit Chimique de France (Paris), v. 19, pp. 483 488. Hatta, Tatsuo (1987), "Le Chtelier principle," The New Palgrave: A Dictionary of Economics, v. 3, pp. 15557.
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Samuelson, Paul A. (1947, Enlarged ed. 1983). Foundations of Economic Analysis, Harvard University Press. ISBN 0-674-31301-1 D.J. Evans, D.J. Searles and E. Mittag (2001), "Fluctuation theorem for Hamiltonian systemsLe Chtelier's principle", Physical Review E, 63, 051105(4). Also refer to Brown Lemay Bursten. 10th or 11e edition for this principle.
External links
YouTube video of Le Chatelier's principle and pressure (http://www.youtube.com/watch?v=YMqyG9QG6oc&feature=related) Retrieved from "http://en.wikipedia.org/w/index.php? title=Le_Chatelier%27s_principle&oldid=581609190" Categories: Equilibrium chemistry Homeostasis This page was last modified on 14 November 2013 at 10:31. Text is available under the Creative Commons Attribution-ShareAlike License; additional terms may apply. By using this site, you agree to the Terms of Use and Privacy Policy. Wikipedia is a registered trademark of the Wikimedia Foundation, Inc., a nonprofit organization.
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