2/14/2012

Chemical Reactions: Are they really complete?

When doing stoichiometry calculations, weve always assumed all reactions proceed to completion.
How much product is made when X reacts with Y to produce Z?

Not always the case, depending on the conditions:

In some reactions, all reactants are converted to product.

Chemical Equilibrium
Chapter 14
1

Reaction proceeds essentially to completion

In some reactions, very little of the reactants are converted to product.

Reaction occurs only to a slight extent

In some reactions, some of the reactants are converted to product.

Reaction stops short of completion

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.

Stoichiometry & Equilibrium

When heated PCl5, phosphorus pentachloride, forms PCl3 and Cl2 as follows: PCl5(g) PCl3(g) + Cl2(g) When 1.00 mol PCl5 in a 1.00-L container is allowed to come to equilibrium at a given temperature, the mixture is found to contain 0.135 mol PCl3. What is the molar composition of the mixture?

Stoichiometry & Equilibrium

PCl5(g) Initial Change Equilibrium 1.00 mol
x

The Equilibrium Constant

Consider the general reaction: For this reaction, the equilibrium constant expression (or equilibrium expression) is:

PCl3(g) + Cl2(g) 0 +x x 0 +x x
5

Square brackets indicate the concentrations of the reactants and products at equilibrium and Kc is the equilibrium constant.

*Derivation of the equilibrium constant from rate law*

1.00 x

2/14/2012

Equilibrium Constant Practice

Methanol (also called wood alcohol) is made commercially by hydrogenation of carbon monoxide at elevated temperature and pressure in the presence of a catalyst: 2H2(g) + CO(g) CH3OH(g) What is the Kc expression for this reaction?
7

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.
8

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.

Le Chateliers Principle & Pressure

When the size of the container decreases, the overall pressure increases. The reaction will shift to reduce the pressurethat is, it will shift toward the side of the reaction with fewer gas molecules. When the size of the container increases, the overall pressure decreases. The reaction will shift to increase the pressure that is, it will shift toward the side with more gas molecules. In the event that both sides of the equilibrium reaction have the same number of moles of gas, pressure has no effect on the equilibrium.
9 10

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)
11

Le Chateliers Principle & Temperature

Changing the temperature changes the value of the equilibrium constant. Changing the temperature can also cause a shift in the equilibrium. The direction of each of these changes depends on the sign of Ho. endothermic reaction, Ho > 0 (positive), we consider that heat is a reactant, high T more favorable exothermic reaction, Ho < 0 (negative), we consider that heat is a product, low T more favorable
12

2/14/2012

Le Chateliers Principle & Temperature

For an endothermic reaction, increasing the temperature increases the value of Kc. For an exothermic reaction, increasing the temperature decreases the value of Kc. Decreasing the temperature has the opposite effect. In addition to the value of Kc, we can consider the direction in which the equilibrium will shift. When heat is added (temperature increased), the reaction will shift to use heat. When heat is removed (temperature decreased), the reaction will shift to produce heat.
13 14

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?
15

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)

16

Reversible Reactions & Kc

For the reaction: aA + bB cC + dD; K1 When the reaction is reversed: cC + dD aA + bB; K2 The equilibrium constant expression is inverted: K2 =

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 =
17 18

2/14/2012

Equilibrium Constants in Terms of Partial Pressures

For reactions involving gases, concentrations are generally reported as partial pressures, and the equilibrium expression is often written:

How are Kc and Kp related?

We know

[A]

nA VA nA P A VA RT

From the ideal gas law,

The partial pressure of each reactant and product are given as Px in units of atmospheres, and Kp is the equilibrium constant when concentration is given in partial pressures.

So,

PA
19

nA RT VA
20

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
21

K p K c RT
2

RT 2

Kc

22

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?

What can the equilibrium constant be used for?

1. 2.

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.

To determine equilibrium concentrations given the initial concentrations and value of Kc .

23

24

2/14/2012

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.

25

26

Predicting the Direction of a Reaction

Nitrogen and oxygen form nitric oxide. N2(g) + O2(g) 2NO(g) If an equilibrium mixture at 25C contains 0.040 M N2 and 0.010 M O2, what is the concentration of NO in this mixture? The equilibrium constant at 25C is 1.0 10-30. Reaction Quotient (Q)
describes the system at a given instant, not necessarily at equilibrium expression is obtained the same way as equilibrium expression

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.

27

28

Qc must move towards Kc

Predicting the Direction of a Reaction

A 10.0 L vessel contains 0.0015 mol CO2 and 0.10 mol CO. If a small amount of carbon is added to this vessel and the temperature is raised to 1000C, will more CO form? The reaction is CO2 (g) + C (s) 2 CO (g) The value of Kc for the reaction is 1.17 at 1000C. Assume that the volume of the gas in the vessel is 10.0 L.

Here the numerator must increase; more products must be produced.

Here the denominator must increase; more reactants must be produced.

29

30

2/14/2012

Calculating Equilibrium Concentrations

Nickel(II) oxide can be reduced to the metal by treatment with carbon monoxide. CO(g) + NiO(s) CO2(g) + Ni(s) If the partial pressure of CO is 100. mmHg and the total pressure of CO and CO2 does not exceed 1.0 atm, will this reaction occur at 1500 K? (Kp = 700. at 1500 K.)

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?

31

32

When initial concentrations and Kc are known, use ICE to find

the equilibrium concentrations.

When the Kc expression is not a perfect square: solving a quadratic equation.

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?

33

34

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.

35