Chemical Equilibrium

Thursday, February 17, 2022 12:03 PM

Just as reactions vary greatly in their speed, they also vary greatly in their extent. Indeed, kinetics and equilibrium apply
to different aspects of a reaction.

Kinetics
• Describes how fast or slow a chemical reaction occurs
• The speed (or rate) of a reaction, the concentration of reactant that disappears (or of product that appears) per
unit time.

Thermodynamics
• Tells whether a reaction is spontaneous or not.
• The reaction will either go to completion or will reach a state of Equilibrium

Equilibrium
• Applies to the extent (or yield) of a reaction, the concentration of reactant and product present after unlimited
time, or when no further change occurs.

Reversible Chemical Reaction

• An equal rate of change for the forward and reverse reaction the equilibrium is achieved (balance)
• A reversible chemical reaction is represented by the equation:

• A reversible chemical reaction reaches a state of equilibrium:

A system at equilibrium is dynamic

• On the molecular level; no further net change is observed because changes in one direction are balanced by
changes in the other.
• A forward reaction means the formation of products and a reverse reaction is the formation of reactants.

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 The Equilibrium Constant

• Consider a reversible reaction with the general reaction:

• At equilibrium, no apparent change in the state of the system is observed. The rates of the forward and reverse
reactions become equal, the concentrations of the reactants and products remain constant over time.

Law of Mass Action.

• The equilibrium constant (K) is expressed as

• The values of a, b, c, and d are those of the coefficients in the balanced chemical equation.
• Note that this is equilibrium, not kinetics.
• The rates of the forward and reverse reactions are equal, NOT the concentrations of reactants and products.
• It should be noted that K is a unitless value and temperature dependent.

The direction of the equilibrium can be predicted by taking into consideration the value of K.

Homogeneous Equilibria

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• Homogeneous equilibrium involves reactants and products that are present in the same phase. An example is the
reaction between nitrogen gas and hydrogen gas:

• The K of gaseous systems can be expressed in terms of the concentrations and the partial pressures of the gases
involved.

• Kc and Kp are related in the equation:

• Where R = 0.0821 L∙atm / mol∙K

• T = absolute temp in K
• A_n = Z_moles of gaseous products – Z_moles of gaseous reactants

Heterogeneous Equilibria

• Heterogeneous equilibrium involves reactants and products that are present in the different phase. An example is
the decomposition of calcium carbonate:

• In heterogeneous equilibrium, pure solid and pure liquid substances do not appear in the K expression because
the molar concentrations of these substances are always constant (having a value equal to 1)

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 Predicting the Direction of a Reaction

• At non-equilibrium conditions (e.g., at the start of a reaction), the instantaneous ratio of the concentrations of the
products and reactants is given by the reaction quotient, Qc. Qc has the same form as the equilibrium expression,
Kc. For a general reversible reaction:

If all species of the reactants and products are present at the start of the reaction, three possibilities may occur:
• Qc > Kc system proceeds from right to left to reach equilibrium
• Qc = Kc the system is at equilibrium
• Qc < Kc system proceeds from left to right to reach equilibrium

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 Le Chatelier’s Principle

• When stress is introduced into a system in equilibrium, the system will adjust to relieve the stress and regain
equilibrium
• When a system at equilibrium is subjected to change with these factors temperature, pressure or volume or other
factors, this will shift or the equilibrium will shift to the part of the reaction where
• For example the addition or change in your system if found in your product so the shift of equilibrium to the other
side of the reaction to counter act the change happen in your chemical reaction

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 Factors that affect Systems in Equilibrium
1. Changes in Concentration (Amount) of either reactants or products
• When a system at equilibrium is disturbed by a change in concentration of one of the components, it reacts in the
direction that reduces the change.
• For example, adding more of the product NH3 (refer to equation below), the equilibrium reaction shifts to the left
or favors the reverse reaction in order to offset the change or stress/disturbance applied.

• Offset = to compensate for, by applying a change in the opposite direction; to counterbalance

• Generally, the effects are the following:

2. Changes in Volume and Pressure

• Changes in pressure can have a large effect on equilibrium systems containing gaseous components.
• Changing the volume of the reaction vessel can cause a large shift in equilibrium position, but only for reactions in
which the number of moles of gas changes.
• Generally, the effects are the following:

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 3. Changes in Temperature
• Of the three types of disturbances that may occur – a change in concentration, pressure, or temperature – only
temperature changes alter K.
• Generally, the effects are the following

1. Adding a Catalyst
• A catalyst lowers the activation energy (Ea) for both forward and reverse reactions.
• It does not change equilibrium constant or shift equilibrium but it makes the system reach equilibrium faster.

Here’s the summary of all the effects that these factors can bring to chemical reactions at equilibrium:

Summary

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