MODULE 3 CHEMICAL EQUILIBRIUM

Reversible Reaction reaction wherein the reactants disappear to form the products (forward reaction) & after some time, products begin to react to form the original reactants (reverse reaction). example of a reversible reaction is the synthesis of methanol, CH 3OH(g). It means that at the same time CH3OH(g) is being formed, it decomposes to produce CO(g) & 2H2(g). CO(g) + 2H2(g) CH3OH(g) forward reaction is CO(g) + 2H2(g) CH3OH(g) reverse reaction is CH3OH(g) CO (g) + 2H2(g) Irreversible Reaction reaction wherein reactants disappear and converted to products completely. example of an irreversible reaction is the decomposition of H2O2(l) to H2O(l) & O2(g) H2O2(l) H2O(l) & O2(g) Chemical Equilibrium the state at which opposing reactions are proceeding at equal rates the rate of the forward reaction (products formed from reactants) is equal to the rate of reverse reaction (reactants are formed form the products) involves different substances as reactants & products N2O4(g) NO2(g) Physical Equilibrium equilibrium between the reactant & product of the same substance but of different phase. H2O(l) H2O(g) The Equilibrium Constant Expression, Keq the ratio of the equilibrium concentrations of the product to the equilibrium concentrations of the reactants raised to a certain power equal to their stoichiometric coefficients at a certain temperature. In the reaction, aA + bB cC + dD

the equilibrium constant expression is written as, Keq = [C]c[D]d [A]a[B]b for the reaction, 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) the equilibrium constant expression (K eq) can be either expressed as Kc = [NO]4[H2O]6 [NH3]4[O2]5 or Kp = (PNO)4(PH2O)6 (PNH3)4(PO2)5 Module 3: Chemical Equilibria Page 1 of 6

notes:

equilibrium constant expressions can be expressed either in terms of equilibrium molar

concentrations (the expression is Kc), or in terms of equilibrium partial pressures (the expression is Kp) in writing equilibrium constant expressions, we do not include the concentrations of pure liquids or pure solids. if K >>> 1; equilibrium favors the formation of product (forward reaction) if K <<< 1; equilibrium favors the formation of reactants (reverse reaction)

Homogeneous & Heterogeneous Equilibria when the equilibrium system involves substances all in the same phase, it is called

when the equilibrium system involves substances in different phases, it is called heterogeneous
equilibria
Practice Exercise 3.1: Write the Kc & Kp expressions for the following & classify them as homogeneous or heterogeneous equilibria: 1. SO2(g) + 2H2S(g) 2H2O(g) + 3S(s) 2. NH3(g) + 5/4O2(g) NO(g) + 3/2H2O(g) 3. 2HNO3(aq) + Ba(OH)2(aq) Ba(NO3)2(aq) + 2H2O(l) 4. Mg(OH)2(s) + CO32-(aq) MgCO3(s) + 2OH-(aq)

homogeneous equilibria

Relationship between Kc & Kp consider the reaction involving gases only, aA(g) + bB(g) cC(g) + dD(g) assuming ideal gas behavior, PV = nRT n/V = P/RT Kp = Kc(RT)n

for systems involving gases only,

where: n = [d+c] [a+b]

Practice Exercise 3.2: In the reaction CO(g) + 2H2(g) CH3OH(g) carried out at 483 K, the following equilibrium concentrations are measured: [CO] = 1.03 M; [CH 3OH] = 1.56 M; [H2]= 0.332 M. Calculate the Kc & Kp of this reaction.

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Practice Exercise 3.3: At a certain temperature, Kc= 1.8 x 104 for the reaction N2(g) + 3H2(g) 2NH3(g). If the equilibrium concentrations of N2 & NH3 are 0.015 M & 2.00 M respectively, what is the equilibrium concentration of H2?

Practice Exercise 3.4: A 5.00 L evacuated flask is filled with 1.86 mol NOBr. After equilibrium is
established at 25C, it is found that there is 0.082 mol of Br 2 present. Determine Kc & Kp for the reaction: 2NOBr(g) 2NO(g) + Br2(g).

Practice Exercise 3.5: Equilibrium involving SO2(g), O2(g) & SO3(g) is important in sulfuric acid production. When a 0.0200 mol sample of SO 3 is introduced into an evacuated 1.52 L vessel at 900 K, 0.0142 mol, SO3 is found to be present at equilibrium. What is the value of K p for the dissociation of SO3(g) at 900 K?

Practice Exercise 3.6: A 0.0240 mol sample of N2O4(g) is allowed to come to equilibrium with NO 2(g) in a 0.372 L flask at 25C. Calculate the amount of N2O4 present at equilibrium. N2O4(g) 2NO2(g) Kc = 4.61 x 10-3 at 25 C Module 3: Chemical Equilibria Page 3 of 6

Relationships Involving Equilibrium Constants & Combining Equilibrium Expressions We invert (take the reciprocal) the value of K when we reverse a chemical equation ex: at 298 K, H2(g) + I2(g) 2HI(g) Keq = 794 2HI(g) H2(g) + I2(g) Keq = 1/794

When we multiply the coefficients in a balanced equation by a common factor (2, 3, , etc),
we raise the equilibrium constant to the corresponding power (2, 3, , etc) ex: at 298 K, H2(g) + I2(g) 2HI(g) Keq = 794 2H2(g) + 2I2(g) 4HI(g) Keq = (794)2 are multiplied to obtain the equilibrium constant for the net reaction ex: at 100 C, step 1: 2NOBr(g) 2NO(g) + Br2(g) Keq = 0.42 step 2: Br2(g) + Cl2 2BrCl(g) Keq = 7.2 net rxn: 2NOBr(g) + Cl2(g) 2NO(g) + 2BrCl(g) Keq = 0.42 x 7.2 = 3.0

When individual reactions are added to obtain a net reaction, the individual equilibrium constants

Practice Exercise 3.7: The Kc for the reaction CO(g) + 2H2(g) CH3OH(g) is 14.5. What is the Kc for the reverse reaction?

Practice Exercise 3.8: The following Kc value is given at 298 K for the synthesis of NH 3(g) from its elements. N2(g) + 3H2(g) 2NH3(g) Kc = 3.6 x 108 What is the value of Kc at the same temperature for the reaction: NH3(g) N2(g) + 3/2H2(g)

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Practice Exercise 3.9: For the reaction NO(g) + O2(g) at 184 C, KC = 7.5 x 102. What is the value of Kc and Kp at 184C for the reaction 2NO2(g) 2NO(g) + O2(g)?

The Reaction Quotient, Q the ratio of the initial concentrations of the product to the initial concentrations of the reactants raised to a certain power equal to their stoichiometric coefficients at a certain temperature. Predicting the Direction of Equilibrium Qc = K c reaction is at equilibrium Qc < K c reaction favors the forward reaction Qc > K c reaction favors the reverse reaction Practice Exercise 3.9: At the start of a reaction, there are 0.249 mol N 2, 3.21 x 10-2 mol H2 & 6.42 x 10-4 mol NH3 in a 3.0 L reaction vessel at 200 C. If the equilibrium constant for the reaction N 2(g) + 3H2(g) 2NH3(g) is 0.65 at this temperature, determine whether the system is at equilibrium. If not, determine the direction at which the reaction will proceed.

Le Chateliers Principle when an equilibrium system is subjected to a change in temperature, pressure or concentration of a reacting species, the system responds by attaining a new equilibrium that partially offsets the impact of the change.

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Factors Affecting the State of Equilibrium: 1. Changes in Concentration - an increase in the concentrations of the reactants will cause the equilibrium to favor the forward reaction; an increase in the concentration of the products will cause the equilibrium to favor the backward reaction. 2. Changes in Temperature - raising the temperature of an equilibrium mixture shifts the equilibrium condition in the direction of endothermic reaction; lowering the temperature causes a shift in the direction of the exothermic reaction. Only changes in temperature can affect the value of the equilibrium constant, K. 3. Changes in Pressure & Volume - a decrease in the volume (hence an increase in pressure) of the equilibrium mixture of gases causes a net reaction in the direction producing fewer moles of gases; an increase in the volume (hence a decrease in pressure) of the equilibrium mixture of gases causes a net reaction in the direction producing more moles of gases 4. Effect of Catalysts -the function of a catalyst is to change the mechanism of a reaction to one having a lower activation energy, hence it has no effect on the condition of equilibrium. Practice Exercise 3.10: Explain how each of the following factors affects the amount of H 2 present in an equilibrium mixture in the reaction 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g) H = -150 J a. increase the temperature of the mixture b. introduce more H2O(g) c. double the volume of the container d. add an appropriate catalyst

Practice Exercise 3.11: Consider the reaction, 2SO3(g) 2SO2(g) + O2(g) H = 198.2 kJ What would be the effect on the position of the equilibrium if: a. the total pressure on the system is increased b. oxygen gas was added to the reaction mixture c. the temperature of the system was lowered d. an inert gas, He, is added to the mixture Solve Problems:.15.9, 15.3, 15.15, 15.7, 15.21, 15.25, 15.31,15.37, 15.43, 15.49; Pages 520 523. General Chemistry: The Essential Concepts, 5th edition by Raymond Chang References: General Chemistry: The Essential Concepts, 5th edition by Raymond Chang Chemistry : 8th edition by Whitten, Davis, Peck and Stanley CHEMISTRY: The Molecular Nature of Matter and Change, 4th ed. by Martin Silberberg

Chemistry: The General Science, 10th ed, by Brown, Le May and Bursten.

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