Beruflich Dokumente
Kultur Dokumente
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.
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 actual value for Keq is determined experimentally at a specific temperature for a specific reaction.
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 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)
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
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
Keq usually is not written with units. Why? The Molarity & Pressures are based on a standard: (1 M or 1 atm.)
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.
(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.
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
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
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
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!!