CHEMICAL EQUILIBRIUM

Chemical Equilibrium - a dynamic system in which two or more opposing chemical

reactions are going on at the same time and at the same rate

- a state in which concentration of reactants and products have no

net change over time

 the rate of forward reaction = rate of reverse reaction

At equilibrium, the HF is ionizing at the same rate that is reforming, so the concentration
Of HF, F- and H3O+ are constant

Physical Equilibrium – balance of competing physical processes

Evaporation vs. Condensation
H2O (l) ⇆ H2O (g)

Liquid + heat ⇆ vapor

Freezing vs Melting
H2O (s) ⇆ H2O (l)

Chemical Equilibrium – balance of two or more chemical reactions

Rate of Reaction

The study of reaction rates and reaction mechanisms is known as chemical kinetics.

What factors affect the rate reaction?

 Frequency of collisions between reactants (concentration effects)
 Energy of th collision needed for effeective collisions between reactants (temperature
and catalytic effects)

Rates of Reaction and Equilibrium

 When an equilibrium is established, each reactant (and product) has a nonzero concentration
and this concentrations are constant with respect to time

 When an equilibrium is established, the limiting regent has a nonzero concentration

 The reactions do not stop at equilibrium. The rates of the forward and reverse reaction are
balanced, so there is no net change in concentrations.
Equilibrium Constant

For every equilibrium reaction,

Aa + bB ⇆ cC + Dd

There is a mass law expression defining the equilibrium constant, Keq :

The mass action expression consists of the product of the products, each raised to the
power given by the coefficient in the balanced chemical equation, over the product of the
reactants, each raised to the power given by the coefficient in the balanced chemical equation.
This mass action expression is set equal to the equilibrium constant, Keq, Kc or simply K.
where brackets [ ] indicate molar equilibrium concentrations
Equilibrium Constants in Terms of Concentration

Example:
2SO2(g) + O2(g) 2SO3(g) K = [SO3]2
[SO 2]2[O2]

Equilibrium Constants in Terms of Partial Pressures

Consider the following general reaction:

kf – rate constant for the forward reaction

kr – rate constant for the reverse reaction

For reactions involving gases, concentrations are generally reported as partial pressures, and the
equilibrium expression is often written:
where the partial pressure of each reactant and product are given as Px in units of atmospheres
(atm), and Kp is the equilibrium constant when concentration is given in partial pressures.
Note: The terms for pure solids or pure liquids do not appear in the equilibrium constant
expression.

– as A and B react to form compound AB, the concentration of A and B decrease while
the concentration of P and Q increase. As [A] and [B] decrease, the rate of the forward
reaction decreases. Likewise, as [P] and [Q] increases, the rate of the reverse reaction
increases. Eventually the reaction reaches a point at which the forward and reverse rates are
the same; compound A and B are in equilibrium. At equilibrium, therefore,

Therefore,

where the square brackets indicates the concentration of reactants and products at
equilibrium.

RELATIONSHIP BETWEEN KC AND KP :

Δn = (no. of moles of gaseous products) – (no. of moles of gaseous reactants)

= (c+d) – (a+b)
MAGNITUDE OF EQUILIBRIUM CONSTANTS

* The value of K is a measure of the completeness of a reaction

If K is very, very large, i.e. K >> 1

– the forward reaction will tend to proceed
– equilibrium is attained only after reactants have been largely converted into products
– equilibrium system will contain mostly products with very little unreacted starting materials

If K is very, very small, i.e. K << 1

– the reaction proceeds hardly at all toward completion
– no reaction will occur in the forward direction
– the equilibrium system will consist almost entirely of unreacted starting materials, with very little in
the way of products

For
Thus, a mixture of N2 and O2 will react to a very small extent to produce NO at
equilibrium.

For
Thus, a mixture of N2 and H2 will almost completely be converted to NH3 at equilibrium.

Reaction Quotient, Q

The reaction quotient, Q, is defined in the same way as the equilibrium constant K c except that the
concentrations in the equilibrium constant expression are not necessarily equilibrium values.

For the reaction,

PREDICTING THE DIRECTION OF A REACTION

1. If Q < K, the reaction will move from left to right (forward reaction) to approach equilibrium. In
this way, Q will increase until it equals K.

2. If Q = K, the system is in equilibrium; no net reaction occurs

3. If Q > K, the reaction will move from right to left (reverse direction) to approach equilibrium. In
this way, Q will decrease until it equals K.

 The magnettude of an equilibrium constant is a measure of the extent or efficiency of the

reaction
 A large Keq (>>1) mens that the relative amount of products compared to reactants are
favored.
 A small Keq (<<1) means that the relative amount of reactants compared to products are
favored.
 Values close to 1 mean that both reactants and products are present in significant amounts.

Types of Equilibria:

1. homogeneous equilibrium – involves both reactants and products in a single phase

Ex. CO(g) + 3 H2 (g) CH4(g) + H2O(g) Kc = [CH4][H2O]

[CO][H 2]3

2. heterogeneous equilibrium – involves reactants and products in more than one phase

For reactions involving liquids and solid, the liquids and solids are not included in the
 equilibrium expression.

Ex1. 3 Fe(s) + 4 H2O(g) Fe3O4(s) + 4 H2(g) K = [H2]4

[H 2O]4

Ex.

Exercises:
Write mass action expressions for the following equations:
a. N2 (g) + 3 H2 (g) 2 NH3 (g)
b. CaCO3 (s) CaO(s) + CO2(g)
c. CO(g) + 2 H2 (g) CH3OH(g)
d. HCl(aq) + CaCO3 (s) CaCl2 (aq) + CO2 (g)
e. 2 Pb(NO3)2(s) 2PbO(s) + 4NO2(g) + O2(g)

Le Chatelier's Principle

Le Chatelier's Principle states that whenever a system at equilibrium is subjected to a stress, then
the equilibrium will shift in a direction so as to relieve that stress.

These stresses and their effects are summarized below:

A. Adding or subtracting a product or reactant

1. if species added is a solid or liquid, there is no effect on a gaseous equilibrium.
2. if species added or subtracted is a gas then:
a. adding species shifts direction away from the species added.
b. subtracting a species shifts direction towards the species removed.
B. Change in volume

1. if volume is decreased, the reaction proceeds towards the side with lesser moles of gas.
2. if volume is increased, the reaction proceeds towards side with more moles of gas.
3. if in the balanced equation there are the same number of moles of gas on both sides, a
volume change will not affect the equilibrium.

 Decrease in volume in a gas phase reaction will increase the pressure of all gases
( reactants and products)
 The balanced equation determines whether the change will cause a shift left to make more
reactant or a shift left to make more reactant or a shift right to make more product.
 The reaction will shift to the side with the smaller number of molecules of gas.

How will a derease in container volume affect the equilibrium concentration of hydrogen in the
reaction:

C. Change in pressure

1. increase in pressure shifts equilibrium in direction of decrease in the number of moles of gas
2. decrease in pressure shifts equilibrium in direction of increase in number of moles of gas.
3. if in the balanced equation there are the same number of moles of gas on both sides, a pressure
change will not affect the equilibrium.
* Pressure change does not apply if the pressure of the system is raised by merely adding an
 inert gas.

D. Change in temperature

1. If forward reaction is endothermic:

a. increase in temperature causes Kc to become larger
b. decrease in temperature causes Kc to become smaller
2. If forward reaction is exothermic:
a. increase in temperature causes Kc to become smaller
b. decrease in temperature causes Kc to become larger

An increase in temperature increases the rate of both the forward and reverse reactions
because of the increase in the kinetic energy of the collisions.

However, the application of heat to increase the temperature favors the reaction where heat is
a reactant ( heat is absorbed).

A + heat ⇆ B ( endothermic reaction)

 Adding heat will shift the equilibrium to the right
A ⇆ B + heat (exothermic reaction)
 Adding heat will shift the equilibrium to the left.

E. Adding a catalyst

A catalyst changes the rate of reaction; but cannot shift the equilibrium in favor of either
products or reactants.
A catalyst is a substance that influences the rate of a reaction but can be fully recovered at the
end of the reaction.
A catalyst does not shift the equilibrium or change the yield of either reactants or products.
A catalyst lowers the energy of activation of the reaction and thus affects the rate of the
reaction.
The activation energy is the minimum energy required for the reaction to occur.

When a “new equilibrium” is established,

a. the rates of forward and reverse reactions are equal again
b. K is again satisfied by the concentration of the reactants and products
Equilibrium will:

lie to the right favors the products K>> 1

lie to the left favors the reactants K<<1