What is equilibrium?

Chemical reactions often reach a balancing point, or equilibrium.

What is equilibrium? (cont.)

A reversible reaction is a chemical reaction that can occur in both the forward and reverse directions, such as the formation of ammonia. N2(g) + 3H2(g) 2NH3(g)

What is equilibrium? (cont.)

How does reversibility affect the production of ammonia?

Decreases in the concentrations of N2 and H2 cause the reaction to slow.

What is equilibrium? (cont.)

The reaction reaches equilibrium in figure d.

What is equilibrium? (cont.)

Chemical equilibrium is a state in which the forward and reverse reactions balance each other because they take place at equal rates. Equilibrium is a state of action, not inaction.

Equilibrium Expressions
Some chemical systems have little tendency to react REACTANTS
products

others go to completion
reactants

PRODUCTS

The majority reach a state of equilibrium with some of the reactants unconsumed.

Equilibrium Expressions (cont.)

The law of chemical equilibrium states that at a given temperature, a chemical system might reach a state in which a particular ratio of reactant and product concentrations has a constant value. The Equilibrium Constant Expression

For aA + bB cC + dD

Equilibrium Expressions (cont.)

The equilibrium constant, Keq, is the numerical value of the ratio of product concentrations to reactant concentrations, with each concentration raised to the power equal to its coefficient in the balanced equation. The value of Keq is constant only at a specified temperature. Keq > 1: Products are favored at equilibrium Keq < 1: Reactants are favored at equilibrium

Equilibrium Expressions (cont.)

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

This reaction is a homogeneous equilibrium, which means that all the reactants and products are in the same physical state.

Equilibrium Expressions (cont.)

When the reactants and products are present in more than one physical state, the equilibrium is called a heterogeneous equilibrium. Ethanol in a closed flask is represented by C2H5OH(l) C2H5OH(g).

Equilibrium Constants
For a given reaction at a given temperature, Keq will always be the same regardless of the initial concentrations of reactants and products.

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

Equilibrium Constants (cont.)

A reaction is in equilibrium when:

A. there are more products than reactants B. the amount of products equals the reactants

A. A C. the rate of the forward reaction is greater than the reverse reaction B. B
D. the rate of the forward and reverse reactions C. C are equal

D. D

The value of the equilibrium constant is constant for a given ____. A. temperature B. pressure

C. volume
D. density

A. B. C. D.

A B C D

Le Chteliers Principle
Le Chteliers Principle was proposed in 1888 and states that:

if stress is applied to a system at equilibrium, the system shifts in the direction that relieves or lessens that stress.

Stress is any kind of change in a system that upsets the equilibrium.

Le Chteliers Principle (cont.)

Adjusting the concentrations of either the reactants or the products puts stress on a system in equilibrium. Adding reactants increases the number of effective collisions between molecules and upsets the equilibrium.

Le Chteliers Principle (cont.)

The equilibrium shifts to the right to produce more products.

Stress is relieved by shifting to the left, converting products to reactants.

Le Chteliers Principle (cont.)

Increasing pressure shifts the system to the left, and more products are formed.

Changing the volume (and pressure) of an equilibrium system shifts the equilibrium only if the number of moles of gaseous reactants is different from the moles of gaseous products.
If the number of gaseous moles is the same on both sides of the balanced equation, changes in pressure and volume have no effect on the equilibrium.

Le Chteliers Principle (cont.)

The reaction between CO and H2 is at equilibrium.

Lowering the piston decreases the volume and increases the pressure.

As a result, more molecules of the products form. Their formation relieves the stress on the system.

Le Chteliers Principle (cont.)

Changes in temperature alter the equilibrium position and the equilibrium constant. If heat is added to an equilibrium system, the equilibrium shifts in the direction in which the heat is used up.

Le Chteliers Principle (cont.)

Any change in temperature results in a change in Keq.

Calculating Equilibrium Concentrations

Equilibrium constants can be used to calculate unknown concentrations of products when other concentrations are known.

The Solubility Product Constant Some ionic compounds dissolve readily in water, and some barely dissolve at all.
The equilibrium constant expression for the dissolving of a sparingly soluble compound is called the solubility product constant, Ksp.

The Solubility Product Constant (cont.)

The solubility product constant expression is the product of the concentrations of the dissolved ions, each raised to the power equal to the coefficient of the ion in the chemical equation.

Fe(OH)2(s) Fe+2(aq) + 2OH-(aq)

Ksp [Fe+2]eq [OH]2eq = [Fe(OH)2]eq

The Solubility Product Constant (cont.)

The Solubility Product Constant (cont.) The values in the table can be used to determine the solubility of a sparingly soluble compound.
This involves an ICE chart:

n i t i a l

h a n g e

q u i l i b r i u m

The Solubility Product Constant (cont.) The values in the table can be used to determine the solubility of a sparingly soluble compound.
Example: Calculate the maximum solubility of iron(III) hydroxide.

http://www.chem.purdue.edu/gchelp/howtosolveit/Equilibrium/Solubility_Products.htm

The Solubility Product Constant (cont.)

Ksp can be used to predict whether a precipitate will form when any two ionic solutions are mixed.

Use the initial concentrations of ions in solution in the solubility product constant expression to calculate Qsp, the reaction quotient.

The Solubility Product Constant (cont.)

Ag2CrO4(s) 2Ag+(aq) + CrO42-(aq) Ksp = [Ag+]eq2 [CrO42-]eq Qsp = [Ag+]02 [CrO42-]0

The Solubility Product Constant (cont.)

If Qsp < Ksp the solution is unsaturated and no precipitate will form. If Qsp = Ksp the solution is saturated and no change will occur. If Qsp > Ksp a precipitate will form, reducing the concentrations of the ions in the solution until the product of their concentrations in the Ksp expression equals the numerical value of Ksp.

The Common Ion Effect

Why is PbCrO4 less soluble in aqueous solution of K2CrO4 than in pure water? The K2CrO4 solution contains CrO42 ions before any PbCrO4 dissolves.

The Common Ion Effect (cont.)

A common ion is an ion that is common to two or more ionic compounds.

The lowering of the solubility of a substance because of the presence of a common ion is called the common ion effect.

The Common Ion Effect (cont.)

Example:
Calculate the solubility of PbCl2 in pure water. Next, calculate the solubility of PbCl2 in 0.05 M NaCl(aq).