Unit 4– Chemical Systems and Equilibrium

7.3: Quantitative Changes in Equilibrium

Systems
Reactions Not at Equilibrium
• For the reaction conditions shown;
2NO2(g) ↔ N2O4(g)
equilibrium is not reached until NO2 concentration
reaches 0.0125 mol/L
The Reaction Quotient, Q
• Reaction quotient (Q): a numerical value
determined by using the same formula as the
equilibrium constant (using data for a
reversible reaction) that may or may not be at
equilibrium.
For: aA + bB ↔ cC + dD:
 Determining the Direction of a Reaction
• The symbols for Q and Keq are placed on a number line
• The reaction will move in the direction from Q to Keq

Keq Q
Determining the Direction of a Reaction

Q1 Q2 Q3 Q4 Q5

Reaction proceeds Reaction proceeds

toward right, toward left,
forming products forming reactants
Determining the Direction of a Reaction
Q>K: Q=K: Q<K: ratio of
ratio of products the system is at products to
to reactants is equilibrium. reactants is too
too large, small, reaction
reaction will will proceed
proceed LEFT to RIGHT to reach
reach equilibrium.
equilibrium.
Example 1: Determining the Direction of a
Reaction
Calculate Q to determine the direction of reaction when
the concentrations are: [CH4]=0.100 M, [CO] = 0.500
M, [H2O] = 0.200 M and [H2] = 0.800 M. The
equilibrium constant for the reaction below is 5.67.
CH4(g) + H2O(g) ↔ CO(g) + 3H2(g)
Example 2: Determining the direction of a
Reaction
In the Haber process for manufacturing ammonia,
nitrogen and hydrogen combine in the presence of a
catalyst: N2(g) + 3H2(g) ↔ 2NH3(g)
At 300oC, the value of Keq for this reaction is 7.3.
The following concentrations of gases are present in
a container at 300oC: [N2] = 0.10 mol/L, [H2] = 0.30
mol/L, and [NH3] = 0.20 mol/L. Is this mixture of
gases at equilibrium? If not, in which direction will
the reaction go to reach equilibrium?
Example 3: Calculating Equilibrium
Concentrations from Initial Concentrations
Carbon monoxide reacts with water vapour to
produce carbon dioxide and hydrogen. At 900oC,
Keq is 4.200. Calculate the concentrations of all
entities at equilibrium if 4.000 mol of each entity
are initially placed in a 1.000 L closed container.
CO(g) + H2O(g) ↔ CO2(g) + H2(g)

Step 1: Calculate concentrations given c = n/v

= 4.000/1.000
Step 2: Calculate the value of Q = 4.000 M
Q = [CO2][H2]/[CO][H2O]
= (4.000)(4.000)/(4.000)(4.000)
= 1.000
Example 3 Continued
Step 3: Set up an ICE chart
CO(g) + H2O(g) ↔ CO2(g) + H2(g)

Initial conc. (mol/L) 4.000 4.000 4.000 4.000

Change in conc. (mol/L)

Equilibrium conc.
(mol/L)

Step 4: Solve for x

Example 3 Continued
Step 5: Calculate the equilibrium concentrations
 Calculations with Imperfect Squares

• The “hundred rule” is an assumption made to

simplify problems:

- If the ratio of [initial concentration of

reactant]/Keq > 100, then x is very small
compared to initial concentration, so it is
considered negligible with respect to the change
from the initial concentration, and x may be
removed from that part of the calculation.
Example 4
Carbon monoxide is a primary starting material in the
synthesis of many organic compounds, including
methanol, CH3OH(l).

At 2000oC, Keq is 6.40 × 10-7 for the decomposition of

carbon dioxide into carbon monoxide and oxygen.
Calculate the concentrations of all entities at
equilibrium if 0.250 mol/L of CO2(g) is placed in a
closed container and heated to 2000oC.

2CO2(g) ↔ 2CO(g) + O2(g)

Example 4 Continued
Step 1: Set up an ICE chart
2CO2(g) ↔ 2CO(g) + O2(g)

Initial conc. (mol/L) 0.250 0.00 0.00

Change in conc. (mol/L)

Equilibrium conc. (mol/L)

Step 2: Solve for x

Example 4 Continued
Step 3: Calculate the equilibrium concentrations

Step 4: Check your work

Problems Involving the Quadratic Equations
• In some cases, the value of Keq is too large to
ignore. The calculations may involve the need
to solve a quadratic equation
ax2 + bx + c = 0
Example 5
N2O4(g) → 2 NO2(g)
If initial concentration of N2O4 is 0.50 M, what are
the equilibrium concentrations if Keq is 0.0059?
Step 1 Set up an equilibrium table
N2O4(g) ↔ 2 NO2(g)
Initial (mol/L) 0.50 0.0
Change (mol/L)
Equilib (mol/L)
Example 5 Continued
Step 2. Substitute into Keq expression and
solve.

This is a QUADRATIC EQUATION

ax2 + bx + c = 0
a = 4, b = 0.0059, c = -0.00295
HOMEWORK
• Read p. 463-480
- Complete p. 444 #31, 33, 34, 35
- p. 451 #53 - 57
- p. 454 # 61 - 64, 68 - 70

Worksheets:
• Equilibrium Constant Worksheet #1
• Equilibrium Constant Worksheet #2
• Equilibrium Calcs with Ice Tables