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Le Chatelier's Principle

Le Chatelier's Principle

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Le Chatelier's principle1
Le Chatelier's principle
In chemistry,
Le Chatelier's principle
, also called
Chatelier's principle
, can be used to predict the effect of achange in conditions on a chemical equilibrium. The principle is named after Henry Louis Le Chatelier andsometimes 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 establishe
.This principle has a variety of names, depending upon the discipline using it. See, for example, homeostasis. It iscommon 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 LeChatelier's principle, thereby explaining the diverse phenomena of receptor activation and desensitization.
[2]
Ineconomics, the principle has been generalized to help explain the price equilibrium of efficient economic systems. Insimultaneous equilibrium systems, phenomena that are in apparent contradiction to Le Chatelier principle can occur;these can be resolved by the theory of response reactions.
Status as a physical law
Le Chatelier's principlequalitatively describes systems of non-instantaneous change; the duration of adjustmentdepends on the strength of the negative feedback to the initial shock. Where a shock initially induces positivefeedback (such as thermal runaway), the new equilibrium can be far from the old one, and can take a long time toreach. In some dynamic systems, the end-state cannot be determined from the shock. The principle is typically usedto describe closed negative-feedback systems, but applies, in general, to thermodynamically closed and isolatedsystems in nature, since the second law of thermodynamics ensures that the disequilibrium caused by aninstantaneous shock must have a finite half-life.
[3]
The principle has analogs throughout Systems theory.
Chemistry
Effect of change in concentration
Changing the concentration of an ingredient will shift the equilibrium to the side that would reduce that change inconcentration. 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 onthe system.This can be illustrated by the equilibrium of carbon monoxide and hydrogen gas, reacting to form methanol.CO + 2 H
2
 
CH
3
OHSuppose we were to increase the concentration of CO in the system. Using Le Chatelier's principle, we can predictthat the amount of methanol willincrease, decreasing the total change in CO. If we are to add a species to the overallreaction, the reaction will favor the side opposing the addition of the species. Likewise, the subtraction of a specieswould cause the reaction to fill the
gap
and favor the side where the species was reduced. This observation issupported 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 removedfrom the solution.
 
Le Chatelier's principle2
Effect of change in temperature
The effect of changing the temperature in the equilibrium can be made clear by incorporating heat as either a reactantor a product. When the reaction is exothermic (ΔH is negative, puts energy out), we include heat as a product, and,when the reaction is endothermic (ΔH is positive, takes energy in), we include it as a reactant. Hence, we candetermine whether increasing or decreasing the temperature would favour the forward or reverse reaction byapplying the same principle as with concentration changes.For example, the reaction of nitrogen gas with hydrogen gas. This is a reversible reaction, in which the two gasesreact to form ammonia:N
2
+ 3 H
2
 
2 NH
3
ΔH = -92 kJ mol
-1
The product contains heat:N
2
+ 3 H
2
 
2 NH
3
+ 92kJThis is an exothermic reaction (hence the minus sign) when producing ammonia. If we were to lower thetemperature, the equilibrium would shift to produce more heat. Since making ammonia is exothermic, this wouldfavour the production of more ammonia. In practice, in the Haber process, the temperature is set at a compromisevalue, so ammonia is made quickly, even though less would be present at equilibrium.In exothermic reactions, increase in temperature decreases the equilibrium constant, K, whereas, in endothermicreactions, increase in temperature increases the K value.
The value of K changes with temperature. In theendothermic reaction N
2
O
4
(g)
2NO
2
(g), theequilibrium position can be shifted by changingthe temperature. When heat is added and thetemperature increases, the reaction shifts to theright and the flask turns reddish brown due to anincrease in NO
2
. When heat is removed and thetemperature decreases, the reaction shifts to theleft and flask turns colorless due to an increase inN
2
O
4
. This demonstrates Le Chatelier
s Principlebecause the equilibrium shifts in the direction thatconsumes energy.
Effect of change in pressure
Changes in pressure are attributable to changes in volume. Theequilibrium concentrations of the products and reactants do not directlydepend on the pressure subjected to the system. However, a change inpressure due to a change in volume of the system will shift theequilibrium.Considering the reaction of nitrogen gas with hydrogen gas to formammonia:N
2
+ 3 H
2
 
2 NH
3
ΔH = -92kJ mol
-1
4 volumes
2 volumesNote the number of moles of gas on the left-hand side and the numberof moles of gas on the right-hand side. When the volume of the systemis changed, the partial pressures of the gases change. If we were todecrease pressure by increasing volume, the equilibrium of the abovereaction will shift to the left, because the reactant side has greaternumber of moles than does the product side. The system tries tocounteract the decrease in partial pressure of gas molecules by shiftingto the side that exerts greater pressure. Similarly, if we were to increasepressure by decreasing volume, the equilibrium shifts to the right,counteracting the pressure increase by shifting to the side with fewermoles of gas that exert less pressure. If the volume is increased becausethere are more moles of gas on the reactant side, this change is moresignificant 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 fewermoles of gas.
[4]
A decrease in pressure due to increasing volume causes the reaction to shift to the side with more
 
Le Chatelier's principle3moles of gas. There is no effect on a reaction where the number of moles of gas is the same on each side of thechemical equation.
Effect of adding an inert gas
An inert gas (or noble gas) such as helium is one that does not react with other elements or compounds. Adding aninert gas into a gas-phase equilibrium at constant volume does not result in a shift.
[4]
This is because the addition of anon-reactive gas does not change the partial pressures of the other gases in the container. While it is true that thetotal pressure of the system increases, the total pressure does not have any effect on the equilibrium constant; rather,it is a change in partial pressures that will cause a shift in the equilibrium. If, however, the volume is allowed toincrease in the process, the partial pressures of all gases would be decreased resulting in a shift towards the side withthe greater number of moles of gas. There is a short form to remember this: LBMF (little boy married fiona); Lstands for less pressure, B - backward reaction, M - more pressure, and F - forward reaction.
Effect of a catalyst
A catalyst has no effect on equilibrium. But speeds up both forward and backward reactions equally.Eg:N2+3 H2
2NH3Here Iron(Fe) and Molybdenum (Mo)are catalysts, but the two catalysts does 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 US economist Paul Samuelson in1947. There the generalized Le Chatelier principle is for a maximum condition of economic equilibrium: Where allunknowns of a function are independently variable, auxiliary constraints
 —
"just-binding" in leaving initialequilibrium unchanged
 —
reduce the response to a parameter change. Thus, factor-demand and commodity-supplyelasticities are hypothesized to be lower in the short run than in the long run because of the fixed-cost constraint inthe short run.
[5]
References
[1]Gall, John (2002).
The Systems Bible
(3
rd
ed.). General Systemantics Press. "
The System always kicks back 
"[2]"The Biophysical Basis for the Graphical Representations" (http:/ 
 
 / 
 
www.
 
bio-balance.
 
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 DevelopingEcosystem". 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][4]Atkins1993, p. 114[5]Samuelson, Paul A (1983).
 Foundations of Economic Analysis
. Harvard University Press. ISBN 0-674-31301-1.

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