Chemical Equilibrium
Equilibrium
Equilibrium is a state in which there are no observable changes as time goes by. When a chemical reaction has reached the equilibrium state, the concentrations of reactants and products remain constant over time, and there are no visible changes in the system. However, there is much activity at the molecular lever because reactant molecules continue to form product molecules while product molecules react to yield reactant molecules. This dynamic situation is the subject of this chapter. Equilibrium is much like a ski resort. Where the number of skiers carried up the mountain on the chair lift is equal to the number coming down the slopes. Although there is a constant transfer of skiers, the number of people at the top and the number at the bottom of the slope do not change.
N2O4(g) (Colorless)
2 NO2(g) (Brown)
The color of molecules can be used in a chemical equilibrium in order to show that the concentration of each reactant or product will remain the same over time once equilibrium is reached.
*Notice that the equilibrium concentration of the below three rxns are all different.
(a) Initially only NO2 is present. (b) Initially only N2O4 is present. (c) Initially a mixture of NO2 and N2O4 are present.
Notice that the ratio of [NO] / [N2O4] gives scattered values but the ratio of [NO2]2 / [N2O4] gives a nearly constant value that averages 4.63 x 10-3.
The magnitude of an equilibrium constant, K, will tell us whether an equilibrium reaction favors the products or reactants. If K is much greater than 1, (for this definition we will define much greater than 1 to be 10 or above), then the equilibrium will lie to the right and favor the products. If K is much less than 1, (for this definition we will define much less than 1 to be 0.10 or below), then the equilibrium will lie to the left and favor the reactants. All of this should make sense due to the math of the equilibrium constant equation: K = [C]c [D]d [A]a [B]b aA + bB cC + dD
Homogeneous Equilibria
Homogeneous Equilibrium applies to reactions in which all reacting species are in the same phase. An example is our previous use of: N2O4(g) 2 NO2(g) The equilibrium constant, K, for this reaction would be: Kc = [NO2]2 [N2O4] The subscript of Kc indicates that the concentrations of the reacting species are expressed in molarity or moles/Liter. Gases can also be expressed in terms of partial pressures. At constant temperature, the pressure, P, of a gas is directly related to the concentration in mol/L of the gas; that is, P = (n/V)RT. Therefore, we can also write the above equilibrium constant, K, as: KP = PNO22 PN2O4
KP = PNO22 PN2O4 PNO2 and PN2O4 are the equilibrium partial pressures (in atm) of N2O4(g) and NO2(g). The subscript KP tells us that the equilibrium concentrations are in terms of pressure. In general, Kc is not equal to KP. But a simple relationship between the two can be derived as follows. Let us consider the following equilibrium in the gas phase: aA(g) bB(g) The equilibrium constant, Kc, is: Kc = [B]b [A]a The equilibrium constant, KP, is: KP = PBb PAa PAV = nART -> PA = nART / V (the same can be done with B) We can substitute the above for PA and PB into the KP in order to relate the it to Kc.
When we substitute the previous information, we get: KP = (nBRT / V)b = (nB / V)b x (RT)b-a (nART / V)a = (nA / V)a Now both nA / V and nB / V have units of mol / L and can be replaced with [A] and [B], so that we know get: KP = [B]b x (RT)Dn [A]a KP = Kc (RT)Dn Where Dn = b a Dn = moles of gaseous products moles of gaseous reactants Since pressures are usually expressed in atm, the gas constant R is given by 0.0821 L x atm / K x mol, and we write the relationship as: KP = Kc (0.0821xT)Dn Notice that if Dn = 0, then KP = Kc
Another example of homogeneous equilibrium, is the ionization of acetic acid in water: CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq) For the above equation, when a solvent (such as water) is involved in a reaction and has a very high concentration, (for example, 55.5 M compared to only 1M for the rest of the reactants and products), the concentration of the solvent is left out of the equilibrium equation because it is considered to remain a constant throughout the reaction with no huge change. Therefore the equilibrium constant, K, is written as: Kc = [CH3COO-][H3O+] [CH3COOH]
Heterogeneous Equilibria
Heterogeneous Equilibrium results from a reversible reaction involving reactants and products that are in different phases. An example is when calcium carbonate is heated in a closed vessel, the following equilibrium is attained: CaCO3(s) CaO(s) + CO2(g) The equilibrium constant, K, for this reaction would be: Kc = [CaO][CO2] [CaCO3] In Kc the prime is to distinguish it from the final form of the equilibrium constant, which we will derive further. The concentration of a solid, is an intensive property and does not depend on how much of the substance is present. For example, the molar concentration (mol/L) of copper at 20oC (density of copper is 8.96 g/cm3) is the same, whether we have 1 gram or 1 ton of the metal: [Cu] = 8.96 g x 1 mol = 0.141 mol = 141 mol 1 mL 63.55 g mL L
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In (a) and (b) notice there are different amounts of CaCO3 and CaO solids, but the equilibrium pressure remains the same for the CO2 gas as long as both of the solids are present in the reaction, this is all that matters.
Multiple Equilibria
Sometimes multiple steps are involved inside of an overall reaction, this means that the products of one reaction will be the reactants for another reaction. A+B C+D C+D E+F At equilibrium we can write the two separate equilibrium constants: Kc = [C][D] And Kc = [E][F] [A][B] [C][D] The overall reaction is the sum of the two reaction: A+B C+D Kc C+D E+F Kc Overall Rxn: A+B E+F Kc The equilibrium constant, Kc, for the overall Rxn is: Kc = [E][F] [A][B]
We can obtain the same expression if we take the product of the expressions for Kc and Kc: Kc x Kc = [C][D] x [E][F] = [E][F] [A][B] [C][D] [A][B] Kc = Kc x Kc We can now make an important statement about multiple equilibria: If a reaction can be expressed as the sum of two or more reactions, the equilibrium constant for the overall reaction is given by the product of the equilibrium constants of the individual reactions. The ionization of diprotic acids in aqueous solution is a perfect example of multiple equilibria problems. The following equilibrium constants have been determined for carbonic acid (H2CO3) at 25oC:
H2CO3(aq) 7 HCO3- (aq) 11 H+(aq) + HCO3- (aq) H+(aq) + CO32- (aq) Kc = [H+][HCO3-] / [H2CO3] = 4.2 x 10Kc = [H+][CO32-] / [HCO3-] = 4.8 x 10-
The Overall Rxn is the sum of the two: H2CO3(aq) 2H+(aq) + CO32- (aq) Therefore: Kc = [H+]2 [CO32-] / [H2CO3] And: Kc = Kc x Kc = (4.2 x 10-7)(4.8 x 10-11)
Le Chateliers Prinicple
Chemical equilibrium represents a balance between forward and reverse reactions. In most cases, this balance is quite delicate. Changes in experimental conditions may disturb the balance and shift the equilibrium position so that more or less of the desired product is formed. Variables that can be controlled experimentally are concentration, pressure, volume, and temperature. There is a general rule which helps us to predict the direction in which an equilibrium reaction will move when a change in a variable occurs. The rule, known as Le Chateliers Principle, states that if an external stress is applied to a system at equilibrium, the system adjusts in such a way that the stress is relieved so that a new equilibrium position will be found. The word, stress means a change in a variable that removes a system from the equilibrium point. A+B C+D To understand how we relieve stress look at the above reaction that is at equilibrium. If more of the B reactant is added to the reaction, the system will be pushed in the opposite direction until a new equilibrium point is reached. The reaction will be pushed to the right, away from the added stress. If D is taken out of the reaction then the system will be pushed towards the missing D in order to reach a new equilibrium point. The reaction would be pushed to the right, towards the missing species.
If Pressure Increases Volume Decreases The reaction will shift in directions of smaller number of moles. Example: 3H2(g) + N2(g) -> 2NH3(g) Shifts from Left to Right
If Volume Increases Pressure Decreases The reaction will shift in directions of larger number of moles. Example: 3H2(g) + N2(g) -> 2NH3(g) Shifts from Right to Left
Changes in Temperature
A change in temperature can change the equilibrium constant. 3H2(g) + N2(g) 2NH3(g) + DH DH = -12 kJ/mol The above exothermic reaction gives off heat. Therefore, if you added more heat to the system. The system will want to get rid of the excess heat and the reaction will shift from Right to Left. Kc = [NH3]2 Is the K going to get smaller or bigger? [H2]3[N2] If you are producing more of [H2]&[N2] Then K will get smaller.
When heat is added: If K gets smaller, the reaction is exothermic. If K gets bigger, the reaction is endothermic. When heat is taken away: If K gets larger, the reaction is exothermic. If K gets smaller, the reaction is endothermic.
Effects of a Catalyst
Remember that a catalyst will not produce more products or reactants. It just changes the rate of the reaction to make it go faster. Therefore, a catalyst will have no effect on an equilibrium constant.
I.R.E. Problems
[HI]2 [H2][I2] . 6. Substitute into Equilibrium Expression: 54.3 = [2x]2 [0.500-x][0.500-x] 5. Write the Equilibrium Expression: Kc =
. 54.3 = [2x]2 [0.500-x][0.500-x] 7. Take the square root of both sides to get: 7.37 = 2x . 0.500 x 8. Solve for x: x = 0.393 M 9. Plug x in to find the final concentrations at equilibrium: [H2] = (0.500 0.393) M = 0.107 M [I2] = (0.500 0.393) M = 0.107 M [HI] = (2 x 0.393) M = 0.786 M 10. Check your answers by plugging the above values in to find that the Kc value is accurate.
From step 6:
[0.0224 + 2x]2 . [0.00623-x][0.00414-x] 7. It is not possible to solve this equation by taking the square root of both sides. Instead, we must first carry out the multiplications: From Step 6: 54.3 =
54.3(2.58 x 10-5 0.0104x + x2) = 5.02 x 10-4 + 0.0896x + 4x2
8. Collect the terms: 50.3x2 0.654x + 8.98 x 10-4 = 0 9. This is a quadratic equation of the form ax2 + bx + c = 0. The solution for the quadratic equation is: x = - b +/- b2 4ac 2a
x = - b +/- b2 4ac 2a Here we have a = 50.3, b = -0.654, and c = 8.98 x 10-4, so that: x = 0.654 +/- (-0.654)2 4(50.3)(8.98 x 10-4) 2 x 50.3 x = 0.0114 M OR x = 0.00156 M The first solution is physically impossible, since the amounts of H2 and I2 reacted would be more than those originally present. The second solution gives the correct answer. Note that in solving quadratic equations of this type, one answer will always be physically impossible, so choosing a value for x is easy. 10. Plug x in to find the final concentrations at equilibrium: [H2] = (0.00623 0.00156) M = 0.00467 M [I2] = (0.00414 0.00156) M = 0.00258 M [HI] = (0.0224 + 2 x 0.00156) M = 0.0255 M
container, and the SO3 dissociates by the reaction: 2 SO3(g) D 2 SO2(g) + O2(g)
In an experiment, 1.00 mol H2, 1.00 mol I2, and 1.00 mol HI are introduced into a 1.00-L container. Calculate the concentrations of all species when equilibrium is reached.