Chem 3 Chemical Equilibrium Lecture Notes Part 1 c!

e-γoT 2010

Introduction

Equilibrium exists when there is a “balance of force”. This force can be in the form of normal and gravitational force
(mechanical), heat transfer (thermal), or in a chemical reaction.

CHEMICAL EQUILIBRIUM

Chemical equilibrium is a state at rest for which the amount of reactants and products present are observed to be
constant. This condition is reached when the rate of formation of product is equal to the rate of its consumption.
Although no observable change is seen in the system, a dynamic process is occurring microscopically.

Looking at the figure below, and based on what you have observed in the first experiment, equilibrium was
determined to be reached when the color of the gas in the syringe is no longer changing.

(Further discussion of the experiment will be appended when all post-lab have been submitted)

Chemical equilibrium can only be achieved by reversible reactions. Recalling the lesson in thermodynamics, a
reaction is said to be reversible when ∆G is equal to zero. Reversibility also depends on temperature. Chemical kinetics
determines the rate in which the reaction will occur. Chemical equilibrium shows the extent at which the reaction will
proceed.

Note: A reversible chemical reaction uses a double headed arrow ( ) in its equation.

Based on the activity done using the pellets, the three conditions at which equilibrium exist was modelled. The
number of pellets transferred corresponds to the rate of the reaction. The number of pellets left corresponds to the
amount of reactants and product. It was concluded that equilibrium was achieved when:
(1) the rate of the forward reaction (transfer of R to P) is equal to the rate of the reverse reaction (transfer of P
to R) (Rateforward = Ratereverse)
(2) the amount of R and P no longer varies even though continues transfer have been made ( amount of R and
P are constant)

The activity also showed one very important concept; equilibrium can be achieved from either direction. Each case in
the activity started with different amounts of R and P, but all of them were able to achieve equilibrium. You can see a
graphical representation of this concept applied to experiment 1 in the following link.
Chem 3 Chemical Equilibrium Lecture Notes Part 1 c!e-γoT 2010

Equilibrium Constant (KEQ) and Reaction Quotient (Q)

A reaction quotient is the term for the ratio of the amount of products in a given system raised to its coefficient over
the amount of reactants raised also to its corresponding coefficient. The value of Q changes in a given reaction until it
reaches equilibrium. At this point Q is equal to the equilibrium constant.

The law of mass action states that when a system reaches equilibrium at a given temperature, the ratio of the
quantities that make up the reaction quotient has a constant numerical value, KEQ.

Equilibrium constant is the value obtained when the equilibrium amounts is substituted to the reaction quotient.
Think of a positive number line, Q corresponds to the number line since it can have any value while KEQ is just a point in
that line.

So another way of determining whether the reaction is in equilibrium or not is by solving for Q.

Note: KEQ of a given reaction only varies with temperature.

The following equations show how KEQ expression can be derived from the Rateforward = Ratereverse.

Forward reaction: N2O4 (g) → 2 NO2 (g) Rate law: Rate = kf [N2O4]
Reverse reaction: 2 NO2 (g) → N2O4 (g) Rate law: Rate = kr [NO2]2

Therefore, at equilibrium,
Ratef = Rater
kf [N2O4] = kr [NO2]2
Rewriting, it becomes

Magnitude of KEQ. The value of the equilibrium constant shows the extent at which a given reaction will take place.
The larger the magnitude (K >>1), the more products are present at equilibrium (product favoured). Is it possible to
have a negative value for KEQ?

Thermodynamic equilibrium constant versus equilibrium constant. Before listing the rules in writing KEQ and Q
expression, it is important to know that the thermodynamic equilibrium constant is expressed using activity. But, for our
lesson, we will only use molar concentration and partial pressures in expressing the amounts of products and reactants
in both KEQ and Q expression.

Rules in writing KEQ and Q expression.

1. amounts is be expressed in terms of molar concentration (for both aqueous and gas) or partial pressure (gas).
2. products are always in the numerator, and the reactants are always in the denominator
3. Coefficients in the chemical equations are the exponents used in the expression
- The stoichiometric coefficient of each molecule or compound is used in place of the experimentally
determined exponents because the reaction is assumed to occur at a fast reversible single step.
4. solids and liquids are not included in the expression, why?
5. unit less
Chem 3 Chemical Equilibrium Lecture Notes Part 1 c!e-γoT 2010

Recall that the amounts used in KEQ are the amounts of reactants and products at equilibrium. These amounts can be
expressed in molar concentration or partial pressure. If the amount of reactants and products at equilibrium is
expressed in molar concentration, then KEQ becomes KC but if the amounts are expressed in partial pressures, it is known
as KP. Is it possible to have a KC expression and not a KP expression? What about the other way around?

Practice writing KC and KP expression for the following reactions:

1. formation of ozone from oxygen gas

2. formation of ammonia from nitrogen and hydrogen gas
3. decomposition of phosphorus pentachloride into phosphorus trichloride and chlorine gas
4. formation of sulphur trioxide from oxygen and sulphur dioxide
5. reaction of the aqueous sodium carbonate and calcium chloride to form solid calcium carbonate and sodium
chloride solution
6. decomposition of solid calcium carbonate into lime and carbon dioxide

Manipulating equilibrium constants

• Reversing an equation causes inversion of K.
• Multiplying by coefficients by a common factor raises the equilibrium constant to the corresponding power.
• Dividing the coefficients by a common factor causes the equilibrium constant to be taken to that root.
• The equilibrium constant for a net reaction made up of two or more steps is the product of the equilibrium
constants for the individual steps.

Relating KC and KP in an equation

- Prove that KP = KC(RT)∆mole of gases
Predicting direction of a reaction to achieve equilibrium

TRICK: First, always write K and Q alphabetically arranged. K Q

If K is greater than, then K > Q, add a line to make an arrow with the greater than sign as the arrowhead. This
shows you the direction of the reaction. K -- > Q
If K is less than, then K < Q, add a line to make an arrow with the less than sign as the arrowhead. This shows
you the direction of the reaction. K < -- Q
If K is equal to Q, then K = Q, use the equal sign as the line and make an arrow head on both sides. This shows
you that the reaction is equilibrium. K < = > Q