CHEMICAL EQUILIBRIUM

Is a dynamic process, not static

The rate of the forward reaction is EQUAL to the rate of the reverse reaction. This means reactants are being formed at the same rate as products are being formed, though no net change occurs. Reactions are reversible, represented by double arrows. The concentrations of reactants and products remain constant with time at constant temperature.

2NO2(g) 2NO(g) + O2(g)

The Equilibrium Expression

We can quantify the equilibrium condition using whats known as the Law of Mass Action. Proposed by Gudberg and Waage in 1864, it says essentially that equilibrium is temperature-dependent; however, it does not change with concentration (think molarity) or pressure. We can use this law to write the equilibrium expression.

Equilibrium Expression
For the following reaction at a specified temperature:

aA + bB cC + dD

[C ] [ D ] K a b [ A] [ B ]

Where K is the equilibrium constant and is unitless. Look familiar? K is Q (the reaction quotient) when a reaction is at equilibrium. When concentrations are used, sometimes its referred to as Kc.

Important things to know about writing Equilibrium Expressions

1.) Pure solids (s) do not appear in the expression 2.) Pure liquids (l) do not appear in the expression

Writing an Equilibrium Expression

Write the equilibrium expression for the reaction:

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

K = ???

[ NH 4 ][OH ] K [ NH 3 ]

So far
Weve used aqueous systems to write equilibrium expressions. Would it look strange to write the concentration of a gas in terms of molarity? It would, but we can. Weird, I know. We can also write the equilibrium expression for a gaseous system in terms of partial pressures. Makes a little more sense to me Heres a little background for Marcus and Ian. The rest of us can take a little nap.

 If you recall the ideal gas law is PV=nRT and rearrange it so that the gas concentration is represented by n/V, then you might see that it is equivalent to P/RT. Therefore, P = (n/V)RT. In other words, the partial pressure of a gas is proportional to its concentration.

Wake Up, Everybody!

The bottom line is that if youre given reactant and product information of gases in terms of partial pressures, then you can calculate the Kp, or equilibrium expression in units of pressure.

Example Problem

H2(g) + I2(g) 2HI(g)

PHI Kp PH 2 PI 2

Write the equilibrium expressions, Kc and Kp, for the reaction:

2NO2(g) 2NO(g) + O2(g)

Kc = ???

[ NO] [O2 ] Kc 2 [ NO2 ]

Kp

PNO PO2 PNO2

2

Write the equilibrium expressions, Kc and Kp, for the reaction:

4NH3(g) + 7O2(g) 4NO2(g) + 6H2O(g)

K = ???

[ NO2 ] [ H 2O] K 4 7 [ NH 3 ] [O2 ]

Kp

PNO2 PH 2O PNH 3 PO2

4 7

Write the equilibrium expressions, Kc and Kp, for the reaction:

S(s) + O2(g) SO2(g)

K = ???

[ SO2 ] K [O2 ]

Kp

PSO2 PO2

Relating Kp to Kc
In many instances, the values of Kp and Kc are different. We can use the politically correct equation to convert between the two. Where Kp is the equilibrium expression in units of pressure Kc is the equilibrium expression in units of concentration R is the universal gas constant = 0.0821 L atm/mol K T is temperature in Kelvin ng is the change in number of moles of gas in going from the reactants to the products = (moles of gaseous products) (moles of gaseous reactants); it can be a negative value if you have more moles of reactants than products

Kp = Kc(RT)ng

Homework

Page 789 #1-2 For each problem, write the pressure AND concentration expressions for gases.

The Equilibrium Position

We can describe a reaction as lying to the right or lying to the left. This reflects the positions of species in the chemical equation. Remember that products exist on the right of a chemical equation, so when we say equilibrium lies to the right we are really saying that there are more products being formed. Lies to the left indicates that more reactants are being formed. Later, well discuss ways in which we can shift equilibrium positions by applying stress to a system. But, for now

The Equilibrium Position

3 factors that determine Equilibrium Position: Initial concentrations of species In terms of molarity, more dissolved solute means more collisions of particles which leads to a faster reaction Relative energies of reactants and products Nature is lazy and tends to expend only the minimum amount of energy necessary Degree of organization of reactants and products Nature is also crazy and tends to favor maximum disorder a.k.a. entropy (coming back at us in Thermodynamics unit)

Who cares about K?

K indicates whether a reaction is product-favored or reactant-favored.
K > 1 indicates product-favored K < 1 indicates reactant-favored

K can be used to calculated unknown concentrations of reactants or products at equilibrium (assuming some are already known).

Product-Favored Equilibrium
Large values for K signify the reaction is product-favored

When equilibrium is achieved, most reactant has been converted to product

Reactant-Favored Equilibrium
Small values for K signify the reaction is reactant-favored

When equilibrium is achieved, very little reactant has been converted to product

Significance of the Reaction Quotient

If Q = K, the system is at equilibrium If Q > K, the system shifts to the left, consuming products and forming reactants until equilibrium is achieved If Q < K, the system shifts to the right, consuming reactants and forming products until equilibrium is achieved

Calculations Using the Equilibrium Expressions

The equilibrium expression for a reaction can be used to calculate K, the equilibrium constant.

Example Problem
In an experiment done at 852 K, the equilibrium concentrations are found to be 3.61 x 10-3 M for sulfur dioxide, 6.11 x 10-4 M for oxygen, and 1.01 x 10-2 M for sulfur trioxide. Calculate the equilibrium constant for this reaction.

2SO2(g) + O2 (g) 2SO3 (g)

[ SO3 ] K 2 [ SO2 ] [O2 ]

Example Problem, Continued

[ SO3 ] K 2 [ SO2 ] [O2 ]

[1.01 10 ] K [3.61 10 3 ]2 [6.11 10 4 ]
2 2

K = 1.28 x 104 at 852 K This reaction is product-favored at 852 K.

Manipulations of K
N2(g) + 3H2(g) 2NH3(g) Kc = [NH3]2 [N2][H2]3 When the stoichiometric coefficients of a balanced equation are multiplied by some factor, K is raised to the power of the multiplication factor. 2N2(g) + 6H2(g) 4NH3(g) Kc = [NH3]4 = Kc2 [N2]2[H2]6 If the reaction is reversed, we take the reciprocal of K. 2NH3(g) N2(g) + 3H2(g) Kc = [N2][H2]3 [NH3]2 If we add equations together, we multiply respective Ks.

Homework
Pages 789-791 #5, 7, 19, 23

Easy Enough?
If you can hang with this, youre in good shape. However, we know that the AP folks are not always so kind as to give us the equilibrium concentrations when they ask us to solve for K. What are we to do? Cry? Thats ugly. Scream? Thats loud. Punch? Thats mean. We can use a RICE table! This is what weve been training for using the McCormick table from the Stoichiometry unit.

RICE Table
RICE stands for
Reaction Initial Concentration (if youre talking molarity, make sure youre working with MOLES PER LITER!) Change in Concentration Equilibrium Concentration

How to Use the RICE Table

Consider this reaction at 298 K: H2O(g) + CO(g) H2(g) + CO2(g) Kc = 2.0

Assuming you start with 8 molecules of H2O and 6 molecules of CO, how many molecules of H2O, CO, H2, and CO2 are present at equilibrium?

H2O(g) + CO(g) H2(g) + CO2(g)

K = 2.0

Step #1: Write the equilibrium expression for the reaction. Here, we already know K, so plug it in:

[ H 2 ][ CO2 ] 2. 0 [ H 2O ][ CO ]

Step #2: We RICE the problem, beginning with the Initial concentrations Reaction:
Initial: H2O(g) + CO(g) H2(g) + CO2(g)

8
-1x 8-x

6
-1x 6-x

0
+1x x

0
+1x x

Change:
Equilibrium:

Step #3: We plug equilibrium concentrations into our equilibrium expression, and solve for x using the quadratic equation. H2O(g) + CO(g) H2(g) + CO2(g) Equilibrium: 8-x 6-x x x

( x)( x) 2.0 (8 x)( 6 x)

x=4

Step #4: Substitute x into our equilibrium concentrations to find the actual concentrations
H2O(g) + CO(g) H2(g) + CO2(g) Equilibrium: 8-x 6-x x x

x=4
Equilibrium: 8-4=4 6-4=2 4 4

What Does It All Mean?

At equilibrium, you have 4 molecules of water, 2 molecules of carbon monoxide, 4 molecules of hydrogen gas, and 4 molecules of carbon dioxide. We can also use the RICE table to solve for equilibrium concentrations and equilibrium pressures.

Homework
Page 790 #13, 15