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Chapter 15

Chemical 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.

Chemical and Physical Equilibrium

Chemical Equilibrium is achieved when the rates of the forward and reverse reactions are equal and the concentrations of the reactants and products remain constant. The change that occurs in a chemical equilibrium is the making and breaking of bonds, which is a chemical change. Chemical Example: N2O4(g) 2 NO2(g) Physical Equilibrium is a result of equilibrium between two phases of a substance. The changes that occur are not chemical, but physical phase changes such as going from a liquid to a gas in the forward direction and the gas to a liquid in the reverse direction. Physical Example: H2O(l) H2O(g)

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.

The Equilibrium Constant, K

The table below shows experimental data for the NO2 N2O4 system at 25 oC. The gas concentrations are expressed in molarity, which can be calculated from the number of moles of the gases present and the volume of the flask in liters.
Initial Concentrations (M) [NO2] [N2O4] Equilibrium Concentrations (M) [NO2] [N2O4] Ratio of Concentrations at Equilibrium [NO2] [NO2]2 [N2O4] [N2O4] . 0.0851 4.65 x 10-3 0.102 4.66 x 10-3 0.0967 4.60 x 10 -3 0.0880 4.60 x 10-3 0.227 4.63 x 10-3 .

0.000 0.0500 0.0300 0.0400 0.200

0.670 0.446 0.500 0.600 0.000

0.0547 0.0457 0.0475 0.0523 0.0204

0.643 0.448 0.491 0.594 0.0898

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 Equilibrium Constant, K

K = [NO2]2 = 4.63 x 10-3 [N2O4] K is a constant for the equilibrium reaction: N2O4(g) 2 NO2(g) Note that the exponent 2 for [NO2] in this expression is the same as the stoichiometric coefficient for NO2 in the reversible reaction. We generalize this phenomenon with the following reversible reaction: aA + bB cC + dD For this particular reaction, the equilibrium constant, K, is: K = [C]c [D]d [A]a [B]b Note that for a reversible reaction at equilibrium and constant temperature, a certain ratio of reactant and product concentrations has a constant value, K (the equilibrium constant). This will remain a constant no matter what the concentrations are, as long as the reaction is in equilibrium!

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

Solids & Liquids in Equilibrium Constants

Because pure solids and pure liquids will always have the same molar concentration no matter how much of the solid exists, they are considered to be a constant and are not used in an equilibrium constant equation. Therefore the final equilibrium constant equation for the previous reaction of calcium carbonate is: Kc = [CO2] Notice there is no prime present because this is the final equilibrium constant equation. The equilibrium constant for the KP is: KP = PCO2 Notice that in both cases, the equilibrium constants do not depend on CaCO3 or CaO solids, as long as some of each is present at equilibrium, this is all that matters.

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

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)

Summary for Writing Equilibrium Constant Expressions

The concentrations of the reacting species in the condensed phase are expressed in mol/L; in the gas phase, the concentrations can be expressed in mol/L or in atm. Kc is related to KP by the equation: KP = Kc(RT)Dn. Where, R = 0.0821 L x atm / K x mol and Temperature is always in Kelvin. The concentrations of pure solids, pure liquids (in heterogeneous equilibria), and solvents (in homogeneous equilibria), do not appear in the equilibrium constant expressions. The equilibrium constants Kc and KP have no units. In quoting a value for the equilibrium constant, we must specify the balanced equation and temperature since the reactions are reversible and can be written in either direction and because the reactions and therefore the equilibrium constants are dependant upon temperature. 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 (multiplication) of the equilibrium constants of the individual reactions.

Predicting the Direction of a Reaction

The equilibrium constant Kc for the formation of hydrogen iodide from molecular hydrogen and molecular iodine in the gas phase: H2(g) + I2(g) 2HI(g) Is 54.3 = Kc at 430 oC. Suppose that in a certain experiment we place 0.243 mole of H2, 0.146 mole of I2, and 1.98 moles of HI all in a 1.00 Liter container at 430 oC. Will there be a net reaction to form more H2 and I2 or more HI? To figure out this question, we insert the starting concentrations in the equilibrium constant expression and mark them with the subscript 0 in order to show they are initial concentrations and the reaction has not yet reached equilibrium. [HI]02 = (1.98)2 = 111 [H2]0 [I2]0 (0.243)(0.146) Because the answer, 111, is greater than Kc = 54.3, this system is not yet at equilibrium. It is greater than 10, therefore the product (HI) is in high amounts and in order to reach equilibrium, the system will need to form more of the reactants, (H2 and I2). The reaction will therefore go from right to left until equilibrium is reached.

Predicting the Direction of a Reaction

For reactions that have not reached equilibrium, such as the formation of HI in the previous example, we obtain the reaction quotient (Qc), instead of the equilibrium constant by substituting in the initial concentrations into the equilibrium constant expression. Just like we already did in the previous example. To determine the direction in which the net reaction will proceed to achieve equilibrium, we compare the values of Qc and Kc. The three possible cases are as follows: 1. Qc > Kc The ratio of initial concentrations of products to reactants is too large. To reach equilibrium, products must be converted to reactants. The system proceeds from right to left, consuming products and forming reactants, until equilibrium is reached. 2. Qc = Kc The system is at equilibrium. 3. Qc < Kc The ratio of initial concentrations of products to reactants is too small. To reach equilibrium, reactants must be converted to products. The system proceeds from left to right, consuming reactants and forming products, until equilibrium is reached.

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.

Changes in Volume and Pressure

Changes in pressure affect the concentration of gases. PV = nRT P = (n/V)RT P and V are inversely proportional: The greater the pressure, the smaller the volume, and the greater the volume, the smaller the pressure. Also notice that (n/V) or molarity is directly proportional to pressure. Therefore, as the pressure increases, the molarity increases and as the pressure decreases, the molarity decreases. In the system: N2O4(g) 2 NO2(g) If the above system is in a closed cylinder with a movable piston, what would happen if we increased the pressure on the gases by pushing down on the piston at constant temperature? The concentration of both of the gases will also increase. Because the equilibrium constant has [NO2]2 in the numerator, then the concentration of NO2 will increase more than the concentration of the N2O4 in the denominator. This means that Qc > Kc and the reaction will shift to the left until Qc = Kc. If the pressure decreases, molarity would decrease and the concentration of [NO2]2 in the numerator decreases more than the denominator, N2O4, and then Qc < Kc and the reaction will shift to the right until Qc = Kc

Gases With Pressure and Volume Effects

1. Pressure and volume change only effects equilibria that has gases in them. AND 2. Only equilibria in which there is a change in the number of moles of gases are effected. Pressure and volume of gases are inversely proportional.

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.

Calculating Equilibrium Concentrations

A mixture of 0.500 mol H2 and 0.500 mol I2 was placed in a 1.00 L stainless-steel flask at 430oC. The equilibrium constant Kc for the reaction: H2(g) + I2(g) 2HI(g) is 54.3 at this temperature. Calculate the concentrations of H2, I2, and HI at equilibrium. 1. Write the reaction: H2 + I2 2HI 2. Initial [M]: 0.500 0.500 0.000 3. Reaction [M]: -x -x +2x 4. Equilibrium [M]: (0.500 x) (0.500 x) 2x
(The x represents the change in concentration)

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:

Using the Quadratic Equation in I.R.E. Problems

For the same reaction in the previous example, suppose that the initial concentrations of H2, I2, and HI are 0.00623 M, 0.00414 M, and 0.0224 M, respectively. Calculate the concentrations of these species at equilibrium. 1. Write the reaction: H2 + I2 2HI 2. Initial [M]: 0.00623 0.00414 0.0224 3. Reaction [M]: -x -x +2x 4. Equilibrium [M]:(0.00623 x) (0.00414 x) (0.0224 + 2x)
(The x represents the change in concentration)

5. Write the Equilibrium Expression:

6. Substitute into Equilibrium Exp:

[HI]2 [H2][I2] 54.3 = [0.0224 + 2x]2 . [0.00623-x][0.00414-x] Kc =

[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

Try doing the following problems:

1. At a particular temperature, 12.0 mol of SO3 is placed into a 3.0-L rigid

container, and the SO3 dissociates by the reaction: 2 SO3(g) D 2 SO2(g) + O2(g)

At equilibrium, 3.0 mol of SO2 is present. Calculate K for this reaction?

2. At a certain temperature, 4.0 mol NH3 is introduced into a 2.0-L container, and the NH3 partially dissociates by the reaction: 2NH3(g) D N2(g) + 3H2(g) At equilibrium, 2.0 mol of NH3 remains. What is the value of K for this reaction? 3. At a particular temperature, K = 1.00 x 102 for the reaction: H2(g) + I2(g) D 2HI(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.