Chapter 5

Chemical Equilibrium
Introduction to Equilibrium
Chemical equilibrium is defined as a state where the reversible process shows that the rate of
the forward reaction is equal to the rate of the reverse reaction.
Reaction Possibilities
There are three possible ways a reaction can go: It can go to completion (reactants products); it
can just not react at all (reactants no reaction); it can occur but not go to completion; it would
instead, reach chemical equilibrium (reactants products).
 Reaction Goes to Completion:

 No Reaction Takes Place:

 Reactions That Appear to Stop Before Reaching Completion:

A reaction constant, K, value would look something like this, 0.15 L/mol·s. The units for a
reaction rate will be moles per liter per second and the units of the reaction constant must
produce the correct units for the reaction rate when multiplied in the equation.
Example:
Calculate the reaction rate for the reaction A(g) + B(g) C(g) + D(g), given the initial
concentrations [A] =0.10 M and [B] = 0.20 M and given the reaction constant,
K = 0.015 L/mol·s.R = k[A][B] = (0.015 )(0.10 )(0.20 ) = 0.00030 mol/L·s
Note: The units for K will be whatever is necessary to make the reaction rate units mol/L·s.
Reaction Rate = KR[C][D], where the products C and D have become the reactants.
When this reaction reaches equilibrium and the two rates become constant and equal,
Rateforward = Ratereverse and KF[A][B] = KR[C][D].
KF[A][B] = KR[C][D]
Algebraic manipulation of the expression yields=Since both KF and KR are constants, then
dividing one constant by another yields another constant. The new constant is called the
equilibrium constant and is symbolized by the capital letter K .
The Equilibrium Constant
The equilibrium constant (K) is a mathematical relationship that shows how the concentrations
of the products vary with the concentration of the reactants.
Sometimes, subscripts are added to the equilibrium constant symbol K, such as Keq, Kc, Kp,
Ka, Kb, and Ksp. If the state of a reactant or product is indicated by (aq) or (g), its
concentration can change but if its state is indicated by (s) or (L), its concentration cannot
change.
a A(g) + b B(g) cC(g) + d D(g),

where the lower case a, b, c, and d are coefficients, the equilibrium constant expression would
be:

[C]c[D]d
𝑲=
[A]a[B]b
Here are example equations and their equilibrium constant expressions.
2 NO2(g)↔ 2NO(g) + O2(g)
CO(g) + 3H2(g) ↔ CH4(g) + H2O(g)
2 TiCl3(s) + 2HCl(g) ↔2TiCl4(s) + H2(g)
P4(s) + 6Cl2(g) c4PCl3(s)

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Sample question 1:
SO2(g) + NO2(g) ↔ SO3(g) + NO(g)
Determine the value of K when the equilibrium concentrations are: [SO2] = 1.20 M; [NO2] =
0.60 M; [NO] =1.6 M; [SO3] = 2.2 M. Are the reactants or products favored? Explain your
answer.
Solution:
K= = 4.9 = 4.9

Sample question 2:
At a given temperature, the reaction CO(g) + H2O(g) H2(g) + CO2(g) produces the following
concentrations at equilibrium: [CO] = 0.200 M; [H2O] = 0.500 M;
[H2] = 0.320 M; [CO2] = 0.420 M. Find K.
Solution:
K= =1.34

Sample Question 3:
For the same reaction and the same temperature as in Sample Question 2, the concentrations
of the substances at equilibrium become: [CO] = ?; [H2O] = 0.100 M; [H2] = 0.100 M; [CO2] =
0.100 M. What is the concentration of CO? Ans: 0.0746M
Sample Question 4:
Consider the following equilibrium system: (Intermediate)
2 NO(g) + Cl2(g) ↔2 NOCl(g)
At a certain temperature, the equilibrium concentrations are as follows:
[NO] = 0.184 mol/L, [Cl2] = 0.165mol/L, and [NOCl] = 0.060 mol/L. What is the equilibrium
constant for this reaction?
Sample Question 5:
For the reaction:
MgCl2(s) + O2(g)↔ MgO(s) + Cl2(g)
The equilibrium constant was found to be 3.86 at a certain temperature. If 0.560 mol O2(g) is
placed in a 1.00L container, what is the concentration of Cl2(g) at equilibrium? (Challenging)
Sample Question 6:
Write the equilibrium constant expressions for each of the following equations: (Intermediate)
(a) CH3NH2(aq) + H2O(L)↔ CH3NH3 (aq) + OH (aq)
(b) 2 CaSO4(s) ↔ 2CaO(s) + 2 SO2(g) + O2(g)
(c) 2 Fe3+ (aq) + 3 S2- (aq) ↔ Fe2 S3(s)
Le Châtelier’s Principle
Le Châtelier’s principle states that when a stress is applied to a system at equilibrium, the
equilibrium will shift in a direction to partially counteract the stress and once again reach
equilibrium.
Effect of Concentration Changes on a System at Equilibrium
Raising or Lowering the Concentration of a Reactant or Product
• Increasing the concentration of a reactant causes the equilibrium to shift to the right
producing more products.
• Increasing the concentration of a product causes the equilibrium to shift to the left
producing more reactants.
• Decreasing the concentration of a reactant causes the equilibrium to shift to the left
producing less products.
• Decreasing the concentration of a product causes the equilibrium to shift to the right
producing more products.
Sample Questions
Sample question: For the reaction: SiCl4(g) + O2(g)↔ SiO2(s) + 2 Cl2(g), what would be the
effect on the equilibrium
system if:
(a) [SiCl4] increases (b) [O2] increases (c) [Cl2] increases

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Solution:
(a) [SiCl4] increases: The equilibrium would shift to the right;
(b) [O2] increases The equilibrium would shift to the right;
[SiCl4] decrease;
(c) [Cl2] increases ,The equilibrium would shift left; [SiCl4] and [O2] increase;
Sample Question: For the reaction: PCl3(g) + Cl2(g) PCl5(g), which way will the equilibrium
shift if:
(a) [PCl3] decreases (b) [Cl2] decreases (c) [PCl5] decreases
Solution:
(a) left (b) left (c) right
Review Questions
1. What is the effect on the equilibrium position if the [reactants] is increased? (Intermediate)
2. What is the effect on the equilibrium position if the [reactants] is decreased? (Intermediate)
3. Which of the following will cause a shift in the equilibrium position of the equation:
2 C8H18(L) + 25O2(g) ↔18H2O(L) + 16CO2(g)
I. increase [C8H18]
II. increase [O2]
III. decrease [CO2]
IV. decrease [H2O]
(a) II and I only
(b) II and III only
(c) II and IV only
(d) I, II, III and IV only
4. Which of the following will cause a shift in the equilibrium position of the equation:
CaCO3(s) ↔ CaO(s) + CO2(g)
I. increase [CaCO3]
II. increase [CO2]
III. decrease [CaO]
IV. decrease [CO2]
(a) II only
(b) I and III only
(c) II and IV only
(d) I, II, III and IV only
5. For the reaction: N2O5(s) ↔NO2(g) + O2(g), what would be the effect on the equilibrium if:
(a) [N2O5] increases
(b) [NO2] decreases
(c) [NO2] increases
(d) [O2] increases (Intermediate)
6. Answer the following questions when [CO] is increased in the following system at
equilibrium. (Intermediate)
Fe2O3(s) + 3CO(g) ↔ 2Fe(s) + 3CO2(g)
a) Write the equilibrium constant expression.
b) Which direction will this equilibrium shift?
c) What effect will this stress have on [CO2]?
7. For the reaction: C(s) + H2O(g) ↔ CO(g) + H2(g), what would be the effect on the equilibrium
system if: (Intermediate)
(a) [H2O] increases
(b) mass of C decreases
(c) [CO] increases
(d) [H2] decreases
The Haber Process and Concentration Change Effects
The reaction between nitrogen gas and hydrogen gas can produce ammonia, NH3. Under
normal conditions, this reaction does not produce very much ammonia. Early in the 20th

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century, the commercial use of this reaction was too expensive because of the small yield of
ammonia.
N2(g) + 3 H2(g) →2 NH3(g) + energy

Fritz Haber, a German chemist working in the early years of the 20th century, applied Le
Châtelier’s principle to help solve this problem. Decreasing the concentration of ammonia, for
instance, by immediately removing it from the reaction container will cause the equilibrium to
shift to the right and continue to produce more product. There were a number of other ways
that Haber used to make as much product as possible.
The Effect of Effect Changes of Pressure on a System at Equilibrium
The General Effect of Increasing Partial Pressures
A second type of stress studied in Le Châtelier’s principle is the effect of changing the pressure
of a system at equilibrium. It should be noted that reactants and products that are in solid,
liquid, or aqueous state are NOT compressible. Boyle’s gas law reminds us that pressure and
volume are inversely related. Keep this in mind as you learn the effect of pressure stresses on
the equilibrium position.
Increasing Pressure Shifts Equilibrium toward Fewer Moles of Gas
When you increase the pressure (by reducing volume) on a reaction at equilibrium, the
equilibrium shift will be toward the side that has the fewer moles of gas.For a gaseous system
at equilibrium, an increase in pressure will cause the equilibrium to shift to the side with the
least number of moles (molecules/particles) of gas.
Sample question: For the reaction: 2 SO2(g) + O2(g) → 2SO3(g) what would be the effect on the
equilibrium system when the pressure increases.
Solution:
2SO2(g) + O2(g) → 2SO3(g)
3 moles gas ↔2 moles gas
Since there are 3 moles of gaseous reactants and 2 moles of gaseous products, the equilibrium
would shift right producing more products, SO 3.
Sample question: For the reaction: 4NH3(g) + 5O2(g) ↔ 4NO(g) + 6H2O(g), what would be the
effect on the equilibrium system if the pressure decreases:
Solution:
4NH3(g) + 5O2(g) ↔ 4NO(g) + 6H2O(g)
9 moles gas→10 moles gas
Since there are nine moles of gaseous reactants and ten moles of gaseous products, the
equilibrium would shift right producing more products.

Increased or Decreased Volume

Increasing the volume of a system will shift the equilibrium to the side with the larger number
of moles of molecules/particles. Or, if an equilibrium system has its volume decreased, the side
with the lesser number of moles of molecules/particles will be favored.
Sample question: For the reaction: PCl5(g) ↔ Cl2(g) + PCl3(g) what would be the effect on the
equilibrium system when (a) the volume increases; (b) the volume decreases
Solution:
(a) When the volume is increased, pressure decreases and the equilibrium will shift toward the
side will more moles of gas. Therefore, [PCl5] will decrease and [Cl2] and [PCl3] will increase.
(b) When the volume is decreased, pressure increases and the equilibrium will shift toward the
side will fewer moles of gas. Therefore, [PCl5] will increase and [Cl2] and [PCl3] will decrease.
The Haber Process and the Effect of Pressure Change
Earlier we discussed the reaction that produces ammonia, NH 3:
N2(g) + 3H2(g) ↔ 2NH3(g)
The Effect of Changing Temperature on a System at Equilibrium
Increase in Temperature
• For a forward endothermic reaction, an increase in temperature shifts the equilibrium toward
the products whereas a decrease in temperature shifts the equilibrium toward the reactant
side.

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• For a forward exothermic reaction, an increase in temperature shifts the equilibrium toward
the reactant side whereas a decrease in temperature shifts the equilibrium toward the product
side.
• Increasing or decreasing the temperature causes the K value to change.
The Effect of Temperature on an Endothermic and an Exothermic Equilibrium System
Temperature Exothermic (- ΔH) Endothermic (+ ΔH)
Increase Temperature Shifts left, favors reactants Shifts right, favors products
Decrease Temperature Shifts right, favors products Shifts left, favors reactants

Sample question: Predict the effect on the equilibrium position if the temperature is increased
in each of the following.
(a) H2(g) + CO2(g) ↔ CO(g) + H2O(g) ΔH = +40 kJ/mol
(b) 2SO2(g) + O2(g) ↔ 2SO3(g) + energy
Solution:
((a) H2(g) + CO2(g) ↔ CO(g) + H2O(g) ΔH = +40 kJ/mol
The reactions will shift right producing more products.
(b) 2SO2(g) + O2(g) ↔ 2SO3(g) + energy
The reactions will shift left producing more reactants.
This table shows how the value of K changes for the endothermic and exothermic reactions.

Sample question: How does an increase in the temperature affect the concentration of the
substance boldfaced in each of the following as well as the value of K?
(a) SO2(g) + energy ↔ S(s) + O2(g)
(b) P4(s) + 10Cl2(g) ↔ 4 PCl5(g) + energy
Solution:
(a) SO2(g) + energy ↔ S(s) + O2(g);. the concentration of SO2 will decrease therefore the
equilibrium constant (K) increases and the products are favored.
(b) P4(s) + 10Cl2(g) ↔ 4 PCl5(g) + energy; the concentration of PCl 5 will decrease, therefore the
equilibrium constant (K) decreases and the reactants are favored
The Effect of a Catalyst on a System at Equilibrium
A Catalyst has No Effect on an Equilibrium Position

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