IEquilibrium constant This page explains what is meant by an equilibrium constai }constants expressed in terms of concentrations, Ke. |ooncept of a dynamic equilibrium, and know what is leterogeneous" as applied to chemical reactions. int, introducing equilibrium It assumes that you are familiar with the meant by the terms "homogeneous" and i t We need to look at two different separately, because the equilibri types of equilibria (homogeneous and heterogeneous) ium constants are defined differently. + Ahomogeneous equilibrium has everything present in the same phase. The usual examples include reactions where everything is a gas, or everything is present in the same solution. + Aheterogeneous equilibrium has thi examples include reactions involving s ings present in more than one phase. The usual ‘lids and gases, or solids and liquids. Ke in homogeneous equilibria (This is the more straightforward case. It applies where everything in the equilibrium mixture is present as a gas, or everything is present in the same solution, \ good example of a gaseous homogeneot rr us equilibrium is the conversion of sulphur dioxid © sulphur trioxide at the heart of the Cont. fe ia ‘act Process: 28029 + Ox) ———=> 28044 4 commonly used liquid example is the esterification reaction between an ic aci an alcohol - for example: ovens xd and 2HxCOOH + CHsCH2OHy = cercoocHacHy9 + 20) Se Scanned with CamScanner‘Writing an expression for Ke ‘We are going to look at a general case with the equation: aA+dB ===> + dD No state symbols have been given, but they will be all (g), or all (I), or all (aq) if the reaction was between substances in solution in water. If you allow this reaction to reach equilibrium and then measure the equilibrium ‘concentrations of everything, you can combine these concentrations into an expression known as an equilibrium constant. |The equilibrium constant always has the same value (provided you don't change the temperature), irrespective of the amounts of A, B, C and D you started with. It is also unaffected by a change in pressure or whether or not you are using a catalyst. ‘The square bratets show ‘concentrations in mol dr, lequiibeum constant (D)9 side of he = (DT aoreroa eth ~ TARBe onthe bot “cshows tatit isin tems of ‘Tha indices are the numbers in fontoteach substance in ‘he chemical equaton. Compare this with the chemical equation for the equilibrium. The convention is that the substances on the right-hand side of the equation are written at the top of the Ke expression, land those on the left-hand side at the bottom. 'The indices (the powers that you have to raise the concentrations to - for example, squared or cubed or whatever) are just the numbers that appear in the equation. Note: If you have come across orders of reaction, don’t confuse this with the powers that appear in the rate equation for a reaction. Those powers (the order of the reaction with respect to each of the reactants) are experimentally determined. They don't Scanned with CamScannernecessarily have any direct connection with the numbers that appear in the equation, You may come across attompts to derive tho axprossion for Ke by writing rate equations for the forward and back reactions, Thoso attempts make the fundamental mistako of obtaining the rate equation from the chomical equation, That's WRONG! You could only do that for the very simple cases whore the reaction took place in a single step represented by the given equation, Georgio Karam contacted mo In July 2015 pointing out that you . can in fact derive the Ke expression for more complicated | reactions by looking at each step of the reaction individually and then combining the results. You will find his article by following this link. If you know about orders of reaction and rate equations, you will find this very easy to follow. The fact that this is possible doesn't, however, seem to me to justify using the derivation in general terms of aA plus bB going to cC and dD, and assuming that the numbers in front of the substances in the overall equation represent orders of reaction, That is dangerously misleading, Some specific examples The esterification reaction equilibrium typical equation might be: HyCOOHy + CHCH2OH] —— CHsCOOCH:CHy + H20y here is only one molecule of everything shown in the equation. That means that all the powers in the equilibrium constant expression are "1", You don't need to write those into the ‘Tha positon of equibxum moves b ha ‘ight you lnavasa tho concontaton ofA, this is a useful way of converting the maximum possible amount of B into C and D. You might 1se it if, for example, B was a relatively expensive material whereas A was cheap and dlentiful. What would happen if you changed the conditions by decreasing the concentration of 47 According to Le Chatelier, the position of equilibrium will move so that the concentration of A ncreases again. That means that more C and D will react to replace the A that has been emoved. The position of equilibrium moves to the left. A+ 28 === C+D ——_———"_ ‘The positon ot equilbium moves to tha left you decease tha concentration at A, This is esssentially what happens if you remove one of the products of the reaction as soon as it is formed. If, for example, you removed C as soon as it was formed, the position of 2quilibrium would move to the right to replace it. If you kept on removing it, the equilibrium, dosIition would keep on moving rightwards - turning this into a one-way reaction. ‘mportant This isn't in any way an explanation of why the position of equilibrium moves in the ways lescribed. All Le Chatelier's Principle gives you is a quick way of working out what happens. —_— Noto: Ifyou know about equilibrium constants, you will find a more detailed ‘explanation of the effect of a chango of concentration by following this link, If Scanned with CamScannerj you don't know anything about equilibrium constants, you should ignore this | link. If you choose to follow it, return to this page via the BACK button on your browser or via the equilibrium menu. Using Le Chatelier's Principle with a change of pressure This only applies to reactions involving gases: Ag + 28 =—— = C@ + Dg What would happen if you changed the conditions by increasing the pressure? According to Le Chatelier, the position of equilibrium will move in such a way as to counteract he change. That means that the position of equilibrium will move so that the pressure is reduced again. Pressure is caused by gas molecules hitting the sides of their container. The more molecules you have in the container, the higher the pressure will be. The system can reduce the oressure by reacting in such a way as to produce fewer molecules. in this case, there are 3 molecules on the left-hand side of the equation, but only 2 on the ight. By forming more C and D, the system causes the pressure to reduce. Increasing the pressure on a gas reaction shifts the position of equilibrium towards the side ith fewer molecules. Ag) + 28) Cy) + D@ ———__—__+ ‘Tha positon of equitfum maves tn ha ight it you nawase hha pressure on te reacton, What would happen if you changed the conditions by decreasing the pressure? The equilibrium will move in such a way that the pressure increases again. It can do that by oroducing more molecules. In this case, the position of equilibrium will move towards the left hand side of the reaction. | Scanned with CamScannerA@ + 28q Ce + 0@ ——_—_ ‘The positon of equifbrum moves to he lett lWyou decease the pressure on the reacton. (hat happens if there are the same number of molecules on both sides of the >quilibrium reaction? n this case, increasing the pressure has no effect whatsoever on the position of the >quilibrium. Because you have the same numbers of molecules on both sides, the equilibrium -an't move in any way that will reduce the pressure again. mportant Again, this isn't an explanation of why the position of equilibrium moves in the ways Jescribed. You will find a rather mathematical treatment of the explanation by following the ink below. Using Le Chatelier's Principle with a change of temperature or this, you need to know whether heat is given out or absorbed during the reaction. Assume hat our forward reaction is exothermic (heat is evolved): A+ 23) === = C + D 4H = -250kKJmott This shows that 250 kJ is evolved (hence the negative sign) when 1 mole of A reacts completely with 2 moles of B. For reversible reactions, the value is always given as if the reaction was one-way in the forward direction. The back reaction (the conversion of C and D into A and B) would be endothermic by exactly the same amount. Scanned with CamScanner250d evolved when A and B react completely give C end D. Sel A+ 28) === = C + D 4H =-250kmott —_—_ ‘250)Jis absorbed when C and D react ‘completely b give A and 8. fhat would happen if you changed the conditions by increasing the temperature? .ccording to Le Chatelier, the position of equilibrium will move in such a way as to counteract the change. That means that the position of equilibrium will move so that the temperature is reduced again. uppose the system is in equilibrium at 300°C, and you increase the temperature to 500°C. low can the reaction counteract the change you have made? How can it cool itself down gain? ‘0 cool down, it needs to absorb the extra heat that you have just put in. In the case we are looking at, the back reaction absorbs heat. The position of equilibrium therefore moves to the left. The new equilibrium mixture contains more A and B, and less C and D. A+ 2B) === = C + D 4H = -250kKmort <—_—_—_—— ‘The posifon of equiibrum moves to he left you inzease the temperate. if you were aiming to make as much C and D as possible, increasing the temperature on a ‘eversible reaction where the forward reaction is exothermic isn't a good idea! at would happen if you changed the conditions by decreasing the temperature? he equilibrium will move in such a way that the temperature increases again. Suppose the system is in equilibrium at 500°C and you reduce the temperature to 400°C. The reaction will tend to heat itself up again to return to the original temperature, It can do that by favouring the exothermic reaction. Scanned with CamScannerhe position of equilibrium will move to the right. More A and B are converted into C and D at he lower temperature. A+ 28) === = C + D OH = -250kJmort or ‘The positon of equibrum moves to the fightlt you decease the temperale. jummary + Increasing the temperature of a system in dynamic equilibrium favours the endothermic reaction. The system counteracts the change you have made by absorbing the extra heat. + Decreasing the temperature of a system in dynamic equilibrium favours the exothermic reaction. The system counteracts the change you have made by producing more heat. Important gain, this isn't in any way an explanation of why the position of equilibrium moves in the ays described. It is only a way of helping you to work out what happens. Note: | am not going to attempt an explanation of this anywhere on the site. To do it properly is far too difficult for this level. It is possible to come up with an explanation of sorts by looking at how the rate constants for the forward and back reactions change relative to each other by using the Arrhenius equation, but this isn't a standard way of doing it, and is liable to confuse those of you going on to do a Chemistry degree. If you aren't going to doa Chemistry degree, you won't need to know about this anyway! Le Chatelier's Principle and catalysts Catalysts have sneaked onto this page under false pretences, because adding a catalyst makes absolutely no difference to the position of equilibrium, and Le Chatelier's Principle doesn't apply to them. Scanned with CamScanner‘his is because a catalyst speeds up the forward and back reaction to the same extent. secause adding a catalyst doesn't affect the relative rates of the two reactions, it can't affect ne position of equilibrium. So why use a catalyst? ‘or a dynamic equilibrium to be set up, the rates of the forward reaction and the back reaction lave to become equal. This doesn't happen instantly. For a very slow reaction, it could take ‘ears! A catalyst speeds up the rate at which a reaction reaches dynamic equilibrium. Scanned with CamScanner