Chemical Equilibrium
Chapter 14
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Equilibrium
Reactions that do not proceed to completion are reversible (products react with each other to form original reactants).
rate of forward reaction = rate of reverse reaction (Chemical Equilibrium) Consider solid-liquid equilibrium of water & ice at STP.
When ice cubes are placed in a glass of water, the ice cubes begin to melt, but some water between the ice cubes freezes, causing the ice cubes to fuse. Both melting and freezing are occurring.
PCl3(g) + Cl2(g) 0 +x x 0 +x x
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Square brackets indicate the concentrations of the reactants and products at equilibrium and Kc is the equilibrium constant.
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Le Chateliers Principle
If a system at equilibrium is disturbed by a change in concentration, pressure, or temperature, the system shifts in equilibrium composition in a way that tends to counteract this change of variable (relieve the added stress). Change in reactant or product concentration
If a species is added to a system at equilibrium, the reaction will proceed to consume part of the added species. If a species is removed from a system at equilibrium, the reaction will proceed to restore part of the species removed.
Changes in the partial pressures of substances are handled the same way.
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Practice
The following reaction is at equilibrium: COCl2(g) CO(g) + Cl2(g) a. Predict the direction of reaction when chlorine gas is added to the reaction mixture. b. Predict the direction of reaction when carbon monoxide gas is removed from the mixture.
Practice
In which direction will each reaction shift when the volume of the reaction container is increased? a. CO(g) + 2H2(g) CH3OH(g) b. 2SO2(g) + O2(g) 2SO3(g) c. COCl2(g) CO(g) + Cl2(g)
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For the reaction: 2H2O(g) 2H2(g) + O2(g); Ho = 484 kJ Would you expect this reaction to be favorable at high or low temperatures?
Equilibrium Constant
Carbon dioxide decomposes at elevated temperatures to carbon monoxide and oxygen: 2CO2(g) 2CO(g) + O2(g) At 3000 K, 2.00 mol CO2 is placed into a 1.00-L container and allowed to come to equilibrium. At equilibrium, 0.90 mol CO2 remains. What is the value of Kc at this temperature?
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Heterogeneous Equilibria
The equilibria described so far involve reactions where all reactants and products are gases. These represent homogeneous equilibria since only one phase is involved. Equilibria involving more than one phase are called heterogeneous equilibria. In Kc the concentrations of solids & pure liquids are constant. Write Kc for the following reaction: H2O(g) + C(s) CO(g) + H2(g)
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More about Kc
For the reaction: aA + bB cC + dD; K1 When the reaction is doubled: 2aA + 2bB 2cC + 2dD; K2 The equilibrium constant expression, K2 , is the square of the equilibrium constant expression, K1: K2 =
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[A]
nA VA nA P A VA RT
So,
PA
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nA RT VA
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Kp
c d C RT D RT PC PD a PA PBb Aa RT a Bb RT b
Kc and Kp
For catalytic methanation, CO(g) + 3H2(g) CH4(g) + H2O(g) the equilibrium expression in terms of partial pressures becomes
Kp
Cc Dd RT c d -a-b Aa Bb
Kp
and
PCH4 PH2O
3 PCO PH2
Cc Dd RT n Kp Aa Bb
Kp = Kc (RT)n
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K p K c RT
2
RT 2
Kc
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Practice
The value of Kc at 227C is 0.0952 for the following reaction: CH3OH(g) CO(g) + 2H2(g) What is Kp at this temperature?
To qualitatively describe the content of the reaction mixture by looking at the magnitude of Kc . To determine the direction in which a reaction will proceed by comparing Kc to Q.
Q uses nonequilibrium values
3.
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Magnitude of Kc
When Kc is very large (>102), the equilibrium mixture is mostly products. When Kc is very small (<10-2), the equilibrium mixture is mostly reactants. When Kc approaches 1, the equilibrium mixture contains appreciable amounts of both reactants and products.
Practice
Kc = 0.82 for a reaction. Describe the composition of the equilibrium mixture.
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When Kc > Q, the reaction proceeds to the right. (product) When Kc < Q, the reaction proceeds to the left. (reactant) When Kc = Q, the reaction is at equilibrium.
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When initial concentrations and Kc are known, use ICE to find the equilibrium concentrations. When the Kc expression is a perfect square: solving a linear equation. Hydrogen iodide decomposes to hydrogen gas and iodine gas. 2HI(g) H2(g) + I2(g) At 800 K, the equilibrium constant, Kc, for this reaction is 0.016. If 0.50 mol HI is placed in a 5.0-L flask, what will be the composition of the equilibrium mixture in molarities?
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Practice
For the reaction: H2(g) + F2(g) 2HF(g); Kc = 1.15 102 3.000 mol of each reactant is put in a 1.500-L vessel. What is the equilibrium concentration of each species? What if 3.000 mol of each species was put in a 1.500 L vessel? Calculate the equilibrium concentration of each species.
N2O4 decomposes to NO2. The equilibrium reaction in the gas phase is N2O4(g) 2NO2(g) At 100C, Kc = 0.36. If a 1.00-L flask initially contains 0.100 M N2O4, what will be the equilibrium concentration of NO2?
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Effect of a Catalyst
A catalyst has no effect on the equilibrium composition of a reaction mixture. A catalyst merely speeds up the attainment of equilibrium.
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