CHEMICAL EQUILIBRIUM Le Châtelier’s Principle. CHEMICAL EQUILIBRIUM A state when the rate of the...

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CHEMICAL EQUILIBRIUM

Le Châtelier’s Principle

CHEMICAL EQUILIBRIUM

A state when the rate of the forward reaction is equal to the rate of the reverse reaction.

A + B C + D

A + B C + D

A + B ⇄ C + D

CHEMICAL EQUILIBRIUM

Dynamic process. Both forward and reverse reactions continue, but there is NO NET CHANGE in the amount of reactants and products.

CHEMICAL EQUILIBRIUM

M

Time

Reactants

Products

Equilibrium

CHEMICAL EQUILIBRIUM

The equilibrium point is actually a point in a reaction where a specific mixture of reactants and products has obtained a minimum energy state – the most stable state. This is a temperature dependent condition.

LE CHATELIER’S PRINCIPLE

When a system at equilibrium experiences a stress, the system responds to relieve that stress by changing the ratio of reactants and products. It shifts right or left!

STRESSORS

Concentration Changes of R or PTemperature ChangesPressure/Volume Changes

Concentration Changes

Concentration changes only affect reactants or products in the aqueous (aq) or gaseous (g) state – pure solids (s) or liquids (l) don’t have concentrations.

System will consume what is added or replace what is removed.

Example 1:

Consider the following reaction:

A (g) + B (g) ↔ C (s) + D (g)

Adding more A will cause the reaction to shift to the right, the direction that consumes A.

Example 2:

Consider the following reaction:

A (g) + B (g) ↔ C (s) + D (g)

Removing some B will cause the reaction to shift to the left, the direction that replaces B.

Example 3:

Consider the following reaction:

A (g) + B (g) ↔ C (s) + D (g)

Adding or removing C has no effect on the equilibrium position, since it is in the solid state.

Example 4:

Consider the following reaction:

A (g) + B (g) ↔ C (s) + D (g)

Which direction do you think it will shift if some D is removed?

Yes, that’s right! To the Right!!

Temperature Changes

Effect depends on whether the reaction is endothermic or exothermic.

Increasing the temperature is like adding energy.

Decreasing the temperature is like removing energy.

Temperature Changes

In endothermic reactions, energy is written on the reactant side:

Energy + A + B C + DIn exothermic reactions, energy is

written on the product side:

A + B C + D + Energy

Example 5:

Consider the following reaction: A + B ↔ C + D + Energy

Is this endothermic or exothermic?

Which way will it shift if the temperature is increased?

Yes, that’s right! To the Left!!

Example 6:

Consider the following reaction: 25 kJ + A + B ↔ C + D

Is this endothermic or exothermic?

Which way will it shift if the temperature is decreased?

Yes, that’s right! To the Left!!

Pressure/Volume Changes

Pressure/Volume changes only affect reactants or products in the gaseous (g) state.

Systems that differ in the number of moles of gaseous reactants and products respond by shifting to a more or less compact state.

Pressure/Volume Changes

Consider the following reaction:

A (g) + B (g) ↔ C (s) + D (g)

How many moles of gaseous reactants/products are represented on each side of the arrow?

2 moles on left; 1 mol on right

Example 7:

A (g) + B (g) ↔ C (s) + D (g)

Yes, that’s right! To the Right!!

Which way will it shift if the volume is decreased? (Pressure increased)

Factors That DO NOT Affect Equilibrium Positions

Adding a CatalystAdding an Inert substance, like

a noble gas.

Affect of Catalyst

Speeds up the rate of establishing equilibrium, but will NOT affect the equilibrium position.

Affect of Inert Substance

Does not change any reactant or product concentration, does not change temperature, does NOT affect any individual gas pressure – thus, NO EFFECT on equilibrium position.

EQUILIBRIUM EXPRESSIONS

An equilibrium expression computes an equilibrium constant, Keq. This constant is the ratio of products to reactants raised to their stoichiometric coefficients once equilibrium has been established. Again, pure solids (s) and liquids (l) are OMITTED from the expression.

EQUILIBRIUM EXPRESSIONS

aA (g) + bB (g) cC ⇄ (s) + dD (g)

[A]a

[D]d

[B]bKeq =

For the following reaction:

EQUILIBRIUM EXPRESSIONS

If K > 1 then it’s products favored.

If K = 1 then it’s neither.

If K < 1 then it’s reactants favored.

Meaning of K:

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