AP-Chemistry

Chapter 13
Chemical Equilibrium
Introduction to Equilibrium

Equilibrium Title Page and TOC | New Jersey Center for Teaching and Learning (njctl.org)
 AP-Learning Objectives

➢ The student is able to, given a set of experimental observations regarding physical,
chemical biological, or environmental processes that are reversible, construct an
explanation that connects the observations to the reversibility of the underlying
chemical reactions or processes.
➢ The student can, given a set of initial conditions (concentrations or partial pressures)
and the equilibrium constant, K, use the tendency of Q to approach K to predict and
justify the prediction as to whether the reaction will proceed toward products or
reactants as equilibrium is approached.

➢ The student can, given a manipulation of a chemical reaction or set of reactions (e.g.
reversal of reaction or addition of two reactions), determine the effects of that
manipulation on Q or K.
 Physical Equilibrium

Physical equilibrium occurs when

there are changes of physical
state (phase) occurring at the
same rate.

For example, a mixture of ice and

water at 0°C is undergoing melting
and freezing simultaneousely.
➢ Chemical Equilibrium

➢ The state where the concentrations of all reactants and products remain
constant with time.
➢ On the molecular level, there is frantic activity. Equilibrium is not static,
but is a highly dynamic situation.
➢ Macroscopically static
➢ Microscopically dynamic
 Chemical Equilibrium
Finally, the
We begin with Then brown colorless and
only colorless gas begins to brown gases are
gas. form. forming at equal
rates.

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 Equilibrium: Introduction
➢ Principles of equilibrium allow us to determine many
aspects of a chemical reaction system
● Whether the products or the reactants are favored
● Which way the reaction will proceed
● The composition of the system when the reaction “ends”

➢ Not all reactions go to completion

 Irreversible Reactions
➢Irreversible reactions
● Reaction continues until reactant(s) are used
up: controlled by stoichiometry
● Products cannot react back to reform reactants
● Reaction goes to “completion”
● Examples
• Burning a piece of paper or
• metabolizing glucose, C6H12O6(s)
 Reversible Reactions
➢ Reaction in which the products of a reaction
can react back to produce the original
reactants. The reaction can go both ways:

Forward reaction

Reverse reaction

➢ Which reaction is FASTER? Forward or Reverse?

➢ EXPLAIN!
 Reversible Reactions (Cont.)
What happens when the rate of the forward reaction
becomes equal to the rate of the reverse reaction?

EQUILIBRIUM!!!
 Equilibrium
➢ No net change in the amount of reactants and products

➢ rate of forward reaction = rate of reverse reaction

➢ equilibrium is a dynamic process

● microscopic change (the forward and reverse reactions)

continues to occur.

● macroscopic change (changes in the quantities of substances) is

no longer occurring.
 Equilibrium (cont.)
➢The equilibrium state is independent of
the direction from which it is
approached.
 The N2O4-NO2 Equilibrium System

➢A sample of pure dinitrogen tetroxide, a colorless gas,

is placed in a sealed container at 100oC.
● Decomposition produces nitrogen dioxide, a reddish-brown
gas. As N2O4 is used up, forward reaction rate decreases.
● N2O4(g) ⬄ 2NO2(g)
➢ As NO2 builds up, the reverse reaction rate increases.
● 2NO2(g) ⬄ N2O4(g)
➢When forward and reverse reaction rates are equal, the
amounts of reactant and product remain the same
● N2O4(g) ⬄ 2NO2(g)
● Each gas is reformed as fast as it is used up!
 The N2O4-NO2 Equilibrium System (cont.)

N2O4(g) → 2NO2(g) 2NO2(g) → N2O4(g)

Both graphs show system starting with different initial amounts of

reactants and products but achieve the same equilibrium from “opposite”
directions.
 Visualizing Equilibrium
➢How do you know when this system has
reached equilibrium?
 Visualizing Equilibrium
➢ How do you know when each system has reached
equilibrium? (Do these graphs show the same thing?)
 Equilibrium Application
The reaction that occurs in a car engine is an exothermic process.
Cooling the engine will shift the reaction to the right, ensuring full
conversion of the gasoline to energy and its waste products.

gasoline + O2 CO2 + H2O + heat

 Equilibrium Constant

➢But what does K “mean?”

● Related to composition of system at equilibrium
● Large value => favors products
● Small value => favors reactants
● Characteristic of a the reaction system
● Changes with temperature
 The Equilibrium Constant Expression in Terms of
Molar Concentrations

➢General reaction equation

● aA + bB ⬄ cC + dD
➢Equilibrium constant expression:

Note* K, Kc, Keq may all be used here!

● [A], [B], [C], [D] are molar concentrations at equilibrium

● Exponents = coefficients in balanced equation
Example 1: Equilibrium Constant Expression
Ammonia can be made from hydrogen and nitrogen

N2(g) + 3H2(g) ⬄ 2NH3(g)

Write the equilibrium expression for this system.

a- 2 NO(g) + O2(g) 2 NO2(g)

b- 4 HCl(g) + O2(g) 2 H2O(g) + 2 Cl2(g)
c- NOCl(g) NO(g) + ½ Cl2(g)
 Answers
➢
➢ Write the equilibrium expression for the following
reaction:
4 NH3(g) + 7 O2(g) 4 NO2(g) + 6 H2O(g)
➢ Equilibrium Constant Calculation

➢ At the equilibrium point in the decomposition of phosphorus pentachloride to

chlorine and phosphorus trichloride, the following concentrations are obtained:
0.010 mol/L PCl5, 0.15 mol/L PCl3 and 0.37 mol/L Cl2. Determine the Keq for the
reaction.

➢ PCl5(g) PCl3(g) + Cl2(g)

➢ 0.001 M 0.15 M 0.37 M

Therefore the Keq value for the reaction is 5.55.

 Equilibrium Constant Calculation

➢ The following equilibrium concentrations were observed for the

Haber process at 127°C: [NH3] = 31 × 10−2 mol/L [N2] = 8.5 ×
10−1 mol/L [H 2] = 3.1 × 10−3 mol/L

➢ N2(g) + 3H2(g) 2NH3(g)

Calculate the value of K at 127°C for this reaction.

 Using Equilibrium Constant to calculate equilibrium concentrations

➢ Gaseous dinitrogen tetroxide is placed in a flask

and allowed to decompose to nitrogen dioxide and
reach equilibrium at 100°C. At 100°C, the value of
Keq is 0.212. If the concentration of dinitrogen
tetroxide at equilibrium is 0.155 mol/L, what is the
concentration of nitrogen dioxide at equilibrium?

➢ N2O4(g) 2 NO2(g)
 Equilibrium Constant Calculation (concentration not given)

At equilibrium at 100oC, a 2.0L flask contains:

209g of PCl5, 0.9g of H2O, 0.750 mol of HCl, and 0.500 mol of
POCl3
Calculate the Keq for the reaction:
PCl5 (s) + H2O (g) 2HCl (g) + POCl3 (g)
 The Equilibrium Constant Expression for Gaseous
Chemical Systems

➢General reaction equation

● aA(g) + bB(g) ⬄ cC(g) + dD(g)
➢Equilibrium constant expression:

● PA, PB, PC, PD are partial pressures of the gases in

atmospheres at equilibrium
● Exponents = coefficients in balanced equation
 Calculating Values of Kp

➢ The reaction for the formation of nitrosyl chloride

2 NO(g) + Cl2(g) 2 NOCl(g) was studied at 25°C. The
pressures at equilibrium were found to be PNOCl = 1.2 atm
PNO = 5.0 × 10-2 atm PCl2 = 3.0× 10-1 atm Calculate the value of
Kp for this reaction at 25°C.

Kp= 1.9 × 103

 Relationship between Kp and Kc

● Where Δng = change in number of moles of gas

● R = gas constant => 0.0821 (L atm)/(mol K)
● T = Kelvin temperature
● Kc = Kp if the number of moles of gaseous product= number of moles of
gaseous reactant since (RT) Δn = (RT) 0 = 1.
➢Example: Find Kp given Kc = 0.0288 for the
following reaction:
➢2SO3(g) ⬄ 2SO2(g) + O2(g)
 Relationship between Kp and Kc
➢ calculate the value of Kp at 25° C for the reaction:
➢ 2 NO(g) + Cl2(g) 2 NOCl(g) Kc = 4.6 x 10-4
R = 0.0821 L atm/ mol K
Changing the Chemical Equation
➢ CHANGING STOICHIOMETRIC COEFFICIENTS when
the stoichiometric coefficients of a balanced equation are
multiplied by some factor, the K is raised to the power of
the multiplication factor Kn
➢ REVERSING EQUATIONS take the reciprocal of K ( 1/K)
➢ ADDING EQUATIONS multiply respective Ks (K1 × K2 ×
K3 …)
 Changing the Chemical Equation
➢ Equilibrium constant expression depends on form of chemical
equation written to describe system

● N2O4(g) ⬄ 2NO2(g)

➢ Changing Coefficients
● K’ = Kn (where n = number by which coefficients are multiplied

● ½ N2O4(g) ⬄ NO2(g)

➢ Reversing Reaction Equation

● K” = 1/K

● 2NO2(g) ⬄ N2O4(g)
 Adding Chemical Equations
If a reaction can be expressed as sum of two or more reactions, K for the
overall reaction is the product of the equilibrium constants of the
individual reactions.

Rxn 1: SO2(g) + ½ O2(g) ⬄ SO3(g) Kp = 2.2

+ Rxn 2: NO2(g) ⬄ NO(g) + ½ O2(g) xK = 4.0
p
Rxn 3: SO2(g) + NO2(g) ⬄ SO3(g) + NO(g) Kp = 8.8

Shows that multiplying K1 expression by K2 expression

yields K3 expression, therefore K1 x K2 = K3
Examples
 Example
➢ The following equilibrium concentrations were observed for the Haber
process at 127°C: [NH3] = 31 × 10-2 mol/L [N2] = 8.5 × 10-1 mol/L [H 2]
= 3.1 × 10-3 mol/L
N2(g) + 3H2(g) 2NH3(g)

➢ a. Calculate the value of K at 127°C for this reaction.

➢ b. Calculate the value of the equilibrium constant at 127°C for the
reaction: 2 NH3(g) N2(g) + 3 H2(g)
➢ c. Calculate the value of the equilibrium constant at 127°C for the
reaction given by the equation: 1/ 2 N2(g) + 3 /2 H2(g) NH3(g)

A: K = 3.8 × 104
B: K’ = 2.6 × 10-5
C: K” = 1.9 × 102
 Heterogeneous Equilibria
➢ Reaction system in which more than one phase
(s,l,g,aq) is present
➢ Examples
● CaCO3(s) ⬄ CO2(g) + CaO(s)
● CO2(g) + H2(g) ⬄ CO(g) + H2O(l)
● I2(s) ⬄ I2(g)
➢ Position of equilibrium does not depend on
amount of solid or liquid as long as some is
present
➢ Terms for pure liquids or solids need not appear
in expression for K
Example 2: Heterogeneous Equilibrium Expression
Write the expression for KP and Kc for

a- CaCO3(s) ⬄ CaO(s) +CO2(g)

b- PbCl2(s) ⬄ Pb+2(aq) +2Cl-1(aq)

c- CO2(g) + H2(g) ⬄CO(g) + H2O(l)

 Summary of Equilibrium Constant Expression Rules

➢ Equilibrium systems may involve gases, pure liquids or

solids, and species dissolved in aqueous solution.
➢ For the equilibrium constant expression:
➢ Gases enter as their partial pressures in atm
➢ Pure liquids or solids do not appear; neither does
solvent for a reaction in dilute solution
➢ Species (ions or molecules) in water solution enter as
their molar concentrations
➢ K depends only on temperature
➢ Catalyst does not change K, but gets you to equilibrium
faster
Example 3: Heterogeneous Equilibrium Expression

Write the equilibrium constant expression for

the following reaction system:

Zn(s) + 2H+(aq) ⬄ Zn2+(aq) + H2(g)

Calculating K or Missing [ ]
 One “Hard” One
N2O4 (g) <=> 2 NO2 (g)
A sample of N2O4 (g) is allowed to come to equilibrium with NO2
(g) in a 750 mL flask. At equilibrium, 38.6 g N2O4 remains and
0.0637 moles of NO2 have been produced . Calculate the
equilibrium constant, Kc, for the reaction.