Ch.

15 Chemical Equilibrium
Consider colorless frozen N2O4. At room temperature, it decomposes to brown NO2: N2O4(g) 2NO2(g). At some time, the color stops changing and we have a mixture of N2O4 and NO2. We now write it like this
N2O4(g) 2NO2(g) Each is constantly being formed at the same rate that it is being consumed. It is therefore a dynamic equilibrium. Chemical equilibrium is the point at which the concentrations of all species are constant.

The Equilibrium Constant

Consider the following reaction:

aA + bB

cC + d D

There are two reactions going on, forward and reverse. The rate of each reaction can be expressed separately: Ratef = kf[A]a[B]b Rater = kr[C]c[D]d

At equilibrium, Rf = Rr orkf[A]a[B]b = kr[C]c[D]d We can rearrange this equation and combine the rate constants into a single constant. We end up with this

Cc Dd K eq A a Bb
where Keq is called the equilibrium constant.

The Equilibrium Constant

If the substances in the reaction are gases, then their concentrations are proportional to their partial pressures according to PV=nRT, so we can express Keq in terms of pressures as well

(PC)c (PD)d Keq = (P )a (P )b A B

(Reminder Molarity = n/V =P/RTand R= 0.0821 Latm/molK)
(Changes in pressure at equilibrium will be explored later in the notes.)

The actual value for Keq is determined experimentally at a specific temperature for a specific reaction.

Facts About Keq

Keq does not depend on initial concentrations of the products or reactants since its only the equilibrium concentrations that we are concerned with!

The larger Keq , the more products are present at equilibrium. If Keq>> 1, then products dominate at equilibrium and equilibrium lies to the right. Conversely, the smaller Keq , the more reactants are present at equilibrium. If Keq << 1, then reactants dominate at equilibrium and the equilibrium lies to the left.

The Magnitude of Equilibrium Constants

 The equilibrium constant of a reaction in the reverse direction is the inverse of the equilibrium constant of the reaction in the forward direction Keq(forward) = 1/Keq(reverse)

More Facts About Keq

N2O4(g) 2NO2(g)

For example:

At 100 C, Keq(forward) = 6.49 At 100 C, Keq(reverse) = 1/6.49 = 0.154 Keq does not depend on the reaction mechanism. The value of Keq varies with temperature. (We will see this later.) The stoichiometry of a reaction that has been multiplied by a number changes the equilibrium constant. Keq gets raised to the power equal to that number. For example: 2 4 Keq = (6.49)2 = 42.12

More Facts About Keq

The equilibrium constant for a net reaction made up of two or more steps is the product of the equilibrium constants for the individual steps.

For example: A + B X + C
X+BD A + 2B C + D

Keq(1) = 2.0
Keq(2) = 5.0 Keq = K1 x K2 = 10.0

When this is written in terms of concentrations at equilibrium Keq=10.0 = [C][D]/[A][B]2

Keq usually is not written with units. Why? The Molarity & Pressures are based on a standard: (1 M or 1 atm.)

More Facts About Keq

If concentrations are used in the equilibrium expression, Keq is sometimes written as Kc. When pressures are used in the expression, Keq it sometimes written as Kp. The equilibrium expression only contains the concentrations of gases or aqueous substances and NEVER solids or pure liquids. Why? - Consider the decomposition of calcium carbonate: CaCO3(s) CaO(s) + CO2(g) - The concentrations of solids and pure liquids are constant. The amount of CO2 formed will not depend greatly on the amounts of CaO and CaCO3 present. Keq = [PCO2]

Note: Although the concentrations of these species are not included in the equilibrium expression, they do participate in the reaction and must be present for an equilibrium to be established!

Changes in Equilibrium
Le Chateliers Principle: If a stress is applied to a system that is already at equilibrium, the equilibrium will shift to reduce the effect of the stress. We will now look at changing various things on a system at equilibrium and discuss how the equilibrium will shift to relieve the stress. (1) Changing Concentrations: A+BC+D

If more [A] is added, the rate of the forward reaction increases to relieve the stress. As this occurs [C] and [D] increase, the rate of the reverse reaction increases and quickly equilibrium is reestablished. At equilibrium Rf = Rr. The concentrations of A, B, C, D have changed but: [C][D] remains constant at a given temperature. [A][B]

Changes in Equilibrium
Changing Concentrations Continued.. A+BC+D If [C] is removed for the system, the rate of the forward reaction will increase to replace the [C] that was removed. As this occurs [D] increases, and [A] and [B] decreases the rate of the reverse reaction increases and quickly equilibrium is re-established. Once again, Keq is the same even though the concentrations are different. (2) Pressure:
ONLY AFFECTS CHEMICAL REACTIONS WHICH INVOLVE GASES

As the pressure on the gaseous system increases, the gaseous substances are compressed, their concentrations and # of molecules/liter increase. The reaction, (forward or reverse), which favors the reduction of the number of molecules per liter will be favored. (Remember, if V, then this would cause P.)

Changes in Equilibrium
Changing pressure continued Example: 2H2(g) + O2(g) 2H2O(g) If pressure is increased by decreasing the volume of the gases in the container at equilibrium, then the forward reaction is favored. Why? - This reduces the # of gas particles from 3 to 2. - Note: If the # of gas particles on both sides of the equation is the
same, then changing pressure has NO EFFECT on the equilibrium.

If an inert gas is added, it WILL NOT change the equilibrium.

(3) Temperature: All chemical reactions either give off heat (exothermic) or take in heat (endothermic). An increase in temperature favors the endothermic reaction; a decrease in temperature favors the exothermic reaction.
The temperature of a reaction will change the value of Keq, but for now, lets just focus on how the equilibrium will shift.

Changes in Equilibrium
Changes in temperature continued
Example: H2 + I2 2HI H = - 25 kJ/mol (exothermic) Another way of looking at the reaction

H2 + I2 2HI + heat
Lowering the temperature favors HI formation. (You can think of it as though we are removing the heat product from the equation.) Raising the temperature favors the reverse reaction. van Hoffs Law: In a system at equilibrium, an increase in heat energy is displaced so that heat is absorbed. (4) Catalyst: A catalyst increases the rate of both the forward and the reverse reaction by decreasing Ea. It has no effect on Keq but does cause equilibrium to be reached more quickly.

Catalysts & Changes in Equilibrium

Predicting the Direction of a Reaction

When given the concentrations of reactants & products and the value of Keq, you can easily predict the direction of a reaction. - Simply plug the given concentrations into the equilibrium equation and calculate the reaction quotient, Q. - If Q > Keq then the reverse reaction must occur to reach equilibrium (i.e., products are consumed, reactants are formed, the numerator in the equilibrium constant expression decreases and Q decreases until it equals Keq). - If Q < Keq then the forward reaction must occur to reach equilibrium. (See Practice Problems for an example.)

Predicting the Direction of a Reaction

 Practice Problem: At a certain temperature, a 1.0 L flask initially contains 0.298 moles of PCl3(g) and 0.0087 moles of PCl5(g). After the system reaches equilibrium, 0.00200 moles of Cl2(g) was found in the flask. Calculate the equilibrium concentrations of the gases in the flask and also the value of Keq. PCl5 decomposes according to the following reactionPCl5(g) PCl3(g) + Cl2(g)
Step 1-- Tabulate initial and equilibrium concentrations (or partial pressures) given.
[PCl5] Initial Change Equilibrium 0.002 M 0.0087 M [PCl3] 0.298 M [Cl2] 0

Calculating Keq

This sort of table goes by the nickname ICEboxget it?

Calculating Keq
Step 2- If an initial and equilibrium concentration is given for a species, calculate the change in concentration.
Step 3- Use stoichiometry on the change in concentration line only to calculate the changes in concentration of all species(Since our reaction occurs in a 1:1:1 ratio, the changes for each species is the same. Only the sign is different on the reactant.) Step 4- Deduce the equilibrium concentrations of all species.
[PCl5]
Initial Change Equilibrium 0.0087 M 0.002 M 0.0067 M

[PCl3]
0.298 M + 0.002 M 0.3 M

[Cl2]
0 + 0.002 M 0.002 M

Step 5- Finally, plug the equilibrium concentrations into the equilibrium equation and solve!

Calculating Keq
Keq = [ PCl3][Cl2]/[PCl5]
Keq = [0.3][0.002]/[0.0067] = 0.08955 0.09
[PCl5] Initial Change 0.0087 M 0.002 M 0.0067 M [PCl3] 0.298 M + 0.002 M 0.3 M [Cl2] 0 + 0.002 M 0.002 M

Equilibrium
This

system of tabulating data will allow you to solve for equilibrium concentrations if you are given Keq

Calculating Keq
Practice Problem #2-- Given this equationH2(g)+ I2(g) 2 HI(g) calculate all three equilibrium concentrations when: [H2]o = [I2]o = 0.200 M and Kc = 64.0
[H2] Initial Change Equilibrium 0.200 M [I2] 0.200 M [HI] 0

x
0.200 x

x
0.200 x

+ 2x
+ 2x

Heres where we use stoichiometry to calculate the changes in the concentrations

Now determine the equilibrium concentrations Now plug them into the equilibrium expression and solve for x

Calculating Keq
Kc = [ HI]2/[H2][I2]
64.0 = [2x]2/[0.200 x][0.200 x] Solving this takes some good algebra skills & maybe even a quadratic equation will have to be solvedYUCK!
Both sides are perfect squares, (done so on purpose), so we square root both sides

to get

8.00 = (2x) / (0.200 - x)

From there, the solution should be easier, and so after some cross-multiplying and dividing, etc x = 0.160 M

This is not the end of the solution since the question was asking for the equilibrium
concentrations, so [H2] = 0.200 - 0.160 = 0.040 M [I2] = 0.200 - 0.160 = 0.040 M [HI] = 2 (0.160) = 0.320 M You can check for correctness by plugging back into the equilibrium expression: Kc = (0.320)2 / (0.040)(0.040) = 64 Since Kc = 64.0 we know that the problem was correctly solved.

The End
Now we get to work on more practice problems!!