Equilibrium

Learning Objectives
Unit 3 – Part I
❑ Explain chemical equilibrium on both a macroscopic and microscopic scale

❑ Write equilibrium expressions for balanced chemical reactions

❑ Add reactions and determine the new overall equilibrium constant (K)

❑ Predict direction and position of equilibria given Q and K

❑ Convert between Kc and Kp

❑ Use ICE tables to solve equilibrium problems

❑ Use Le Châtelier’s Principle to predict shifts in equilibrium systems

❑ Explain why temperature affects the equilibrium constant

❑ Use the van’t Hoff equation to calculate equilibrium constants at different

temperatures
 Chemical Equilibrium: 𝐍𝟐 𝐎𝟒 𝑔 ⇋ 𝟐 𝐍𝐎𝟐 𝑔

time0 time1 time2

What is happening to the concentration over time?

time0 – All N2O4(colourless) and no NO2.
time1 – [N2O4] decreases, [NO2] increases. Brown colour is observed.
time2 – Concentrations stabilize

What is happening to the reaction rate over time?

…
…
…?
time3
 Chemical Equilibrium

What is chemical equilibrium?

Reactant and product concentrations stop changing!

Rate of the forward reaction = rate of the reverse reaction

𝐤 𝐟 𝐍𝟐 𝐎𝟒 = 𝐤 𝐫 𝐍𝐎𝟐 𝟐

When does a reaction reach equilibrium?

Depends on the equilibrium constant (K)

How long does it take to reach equilibrium?

Depends on the reaction rates (see Kinetics… later ☺)

Explain chemical equilibrium on both a macroscopic and microscopic scale

Equilibrium Expression: Kc and Kp

a A 𝑎𝑞 + b B 𝑎𝑞 ⇌ c C 𝑎𝑞 + d D 𝑎𝑞
c d
Products C D
Kc = = a b
Reactants A B
where [X] is the concentration at equilibrium

aA 𝑔 +bB 𝑔 ⇌cC 𝑔 +dD 𝑔

Pproducts c d
PC PD
Kp = = a b
Preactants PA PB
where P is the partial pressure at equilibrium

Write equilibrium expressions for balanced chemical reactions

 Equilibrium Expression: Kc versus Kp

How is Kp different from Kc?

• Pressures instead of concentrations.
• Can relate Kp to Kc through the ideal gas law
Kp = Kc×(RT)Δn
– ∆n is the difference between the number of moles of reactants and moles
of products in the gaseous state
– T is in Kelvin
– R = 0.0821 (L•atm)/(K•mol)

How many different K’s are there?

• K or Keq (most general/generic, only typically used for definition
purposes, never use when referring to a specific question)
Kc Kp Ka Kb Kw Ksp Kf

Write equilibrium expressions for balanced chemical reactions

 Example 3.1: Equilibrium Expressions
What is the equilibrium expressions, KC and KP, for:
A. NH3 (aq) + H2 O(l) ⇌ NH4+ (aq) + OH − aq

B. CH4 g + 2 O2 g ⇌ CO2 g + 2 H2 O l

Write equilibrium expressions for balanced chemical reactions

 Example 3.2: KC & KP
For which of the following reactions do KC and KP have the same
numerical value (i.e., KC = KP)?
1
A. CO g + O2 (g) ⇌ CO2 g
2

B. H2 O l + CO g ⇌ H2 (g) + CO2 (g)

C. N2 g + 3 F2 g ⇌ 2 NF3 (g)

D. F2 g + H2 g ⇌ 2 HF(g)

Write equilibrium expressions for balanced chemical reactions

 Example 3.3: From KC to KP
Determine the KP value given the following information:
N2 O4 g ⇌ 2 NO2 g KC = 5.90 × 10−3 at 298 K

Convert between Kc and Kp

 Properties of Equilibrium Constants (K)

1. K is related to the stoichiometry of the balanced chemical equation.

2. K applies only at equilibrium.

3. K is independent of initial conditions.

Consider:
aA g + bB g ⇌ cC g

𝑃𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑃𝐶 𝑐
Kp = =
𝑃𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝑃𝐴 𝑎 𝑃𝐵 𝑏

Can we write the reaction in reverse?

Can we double (or triple, etc…) all of the coefficient values?
Add reactions and determine the new overall Keq
 Adding Equilibrium Reactions

Reaction 1: aA + bB ⇌ cC
c
C
K1 = a b
A B
Reaction 2: cC + dD ⇌ eE + fF
EeFf
K2 =
CcDd
Overall: aA + bB + dD ⇌ eE + fF

Add reactions and determine the new overall Keq

 Example 3.4: Adding Equilibrium Reactions
Given the following chemical reactions with their respective
equilibrium constant (K1 and K2), predict the value of the equilibrium
constant for the reaction.
2A s ⇌3D g
1
Given: A s ⇌ B g + C(g) K1 = 0.0334
2
3D g ⇌B g +2C g K 2 = 2.35

Add reactions and determine the new overall Keq

What is the meaning of K?

𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬
𝐊=
𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬
 What can we do with K?

• Use K to predict the extent of a reaction

– Tell’s us about what will be present at equilibrium

• Use information about the reaction to calculate K’s

• Predict the direction a reaction will proceed in

– Comparing reaction quotients (Q) and equilibrium constants (K)

• Predict how an equilibrium system will respond to stresses

– Le Châtelier's principle

• Calculate properties for systems not under standard conditions

(electrochemistry and thermodynamics… later ☺)
 Identifying Reaction Directions

Do chemical reactions always ‘go forward’?

𝐂𝐇𝟒 𝐠 + 𝐇𝟐 𝐎 𝐠 ⇌ 𝐂𝐎 𝐠 + 𝟑 𝐇𝟐 𝐠 𝐊 𝐜 = 𝟎. 𝟐𝟔

A. 1.0 M 1.0 M 0M 0M

B. 0M 1.0 M 1.0 M 1.0 M

C. 1.0 M 1.0 M 1.0 M 1.0 M

D. 0.1 M 1.0 M 1.0 M 0.1 M

Predict direction and position of equilibria given Q and K

 The Reaction Quotient, Q

Need to compare Q and K!

Q is written the same way as K, but the [ ]’s and P’s are
not necessarily at equilibrium

Predict direction and position of equilibria given Q and K

 Example 3.5: K vs Q
In the hypothetical chemical equilibrium
A g + 2 B g ⇌ 3 C(g) K c = 2.5 × 10−2
If you mix 5.0 mol of each gas in a 1.0 L container, which direction
will the reaction initially proceed? Will the equilibrium conditions be
reactant, or product favoured?

Predict direction and position of equilibria given Q and K

 Example 3.6: Solving Equilibrium Problems
An evacuated flask is charged with 4.40 atm of BrF5 gas at 1000 K.
The system is allowed to come to equilibrium at which point the
total pressure in the flask is 5.20 atm. Determine the value of Kp for
this reaction at 1000 K.
2 BrF5 ⇌ Br2 + 5 F2

Solving Hint
Having an equilibrium problem? Throw RICE at it and it’ll solve itself!
Use ICE tables to solve equilibrium problems
 Example 3.7: Find Equilibrium Concentrations
1.0 mol of H2 and 1.0 mol of I2 were placed in a 1.00 L contained and
heated to 445 °C. Determine all equilibrium concentrations.

H2 g + I2 g ⇌ 2 HI g K c = 25 (at 445 C)

Use ICE tables to solve equilibrium problems

 The Le Chatelier’s Principle states…

“when we make changes to a reaction at equilibrium, the

equilibrium will respond to the change we make to try and
undo the change.”

Common Changes (or stresses):

• Adding or removing substances
• Changing the temperature
• Changing the total pressure or volume
• Adding a catalyst / inert gas

This is an online self-study topic. During lecture, we will only look at

some interesting examples applying this knowledge…
 Example 3.8: A Typical Exam Question
Consider the following initial chemical equilibrium,

FeO s + CO g ⇌ Fe s + CO2 (g) ΔH° = −198 kJ

Complete the following table by writing in if the specified quantity

Increases, Decreases, or No Change?
Stress [CO2] mass Fe K

[CO] is increased

FeO is increased

PCO is decreased

T is increased
 Example 3.9: Three Equilibria
Consider the following three equilibrium:
Reaction 1: NH3 𝑔 + 2 O2 𝑔 ⇌ HNO3 𝑙 + H2 O 𝑙
Reaction 2: CO2 𝑔 + CF4 𝑔 ⇌ 2 COF2 𝑔
Reaction 3: C 𝑠 + H2 O 𝑔 ⇌ CO 𝑔 + H2 𝑔

1. How will increasing the volume of each of these equilibrium

shift the chemical equilibrium?

2. How will adding an inert gas, like xenon, affect each of these
chemical equilibria?
 Example 3.10: Good Ol’ Haber Process
What effect will be spraying liquid water into a system have if NH3 is
far more soluble in water then N2 or H2?

N2 g + 3 H2 g ⇌ 2 NH3 g ΔH°rxn = 92 kJ/mol

A. Adding a catalyst.
B. More NH3(g) will form.
C. More N2(g) will form.
D. Less NH3(g) will form.
E. None of these.
 Example 3.11: Le Châtelier’s Principle
Rising atmospheric CO2(g) concentrations doesn’t just affect the
atmosphere, but bodies of water as well via the following equilibrium
series…

CO2 𝑔 + H2 O 𝑙 ⇌ H2 CO3 𝑎𝑞 𝚫𝐇°𝒓𝒙𝒏 < 𝟎

H2 CO3 𝑎𝑞 + H2 O 𝑙 ⇌ H3 O1+ 𝑎𝑞 + HCO1−

3 𝑎𝑞
𝚫𝐇°𝒓𝒙𝒏 > 𝟎

1. If you recall from CHEM 12 (or equivalent) greater [H3O1+]

means a more acid solution. What happens to the acidity of the
oceans as the atmospheric [CO2] rises?

2. How does temperature affect these equilibrium?

Solubility
Learning Objectives
Unit 3 – Part II
❑ Define Ksp

❑ Perform calculations involving Ksp

❑ Determine the solubility of a compound

❑ Determine whether ions can be separated by precipitation

❑ Predict if precipitate formation will occur

❑ Explain the effect of pH, temperature, and common ions on solubility

 Another K: What is Ksp?

Ksp is the solubility product for a solubility equilibrium

CaCO3 s ⇌ Ca2+ aq + CO2−

3 aq

Molar solubility Solubility

Define Ksp and Kf

 Example 3.12: Calculations with Ksp
What is the molar solubility of CaCO3 in following condition? Ksp of
CaCO3 is 3.3×10−9.
A. In pure water?

B. In a solution that has a [CO32−] of 0.010 M?

Perform calculations involving Ksp and Kf

Determine the solubility of a compound
Explain the effect of pH, temperature, and common ions on solubility
 Example 3.13: Solubility
How many moles of XF2 will dissolve in 2.0 L of water if Ksp for XF2
is 3.2 × 10−11?
A. 2 × 10−4
B. 2.5 × 10−4
C. 3 × 10−4
D. 4 × 10−4
E. 6 × 10−6

Perform calculations involving Ksp and Kf

Determine the solubility of a compound
 Example 3.14: What went wrong?
The Ksp for Fe(OH)3 is 1.6×10−39. On an exam, all the students in the
class determined the molar solubility of Fe(OH)3 to be 8.8×10−11 M
at neutral solution. They were all incorrect. How did they determine
this answer, why is it incorrect, and what is the correct answer?

Perform calculations involving Ksp and Kf

 Example 3.15: Qualitative Solublity
In which of the solutions below is CaCO3 the most soluble?
A. water
B. 0.20 M CaCl2
C. 0.20 M HCl
D. 0.20 M Na2CO3
E. 0.20 M NaCl

Perform calculations involving Ksp and Kf

Determine the solubility of a compound
Explain the effect of pH, temperature, and common ions on solubility
 Example 3.16: pH & Solubility
At a certain temperature, a saturated solution of Zn(OH)2 has a pH
of 8.0. The value of Ksp for Zn(OH)2 is:
A. 2 × 10−12
B. 1 × 10−18
C. 4 × 10−18
D. 5 × 10−19
E. 5 × 10−27

Perform calculations involving Ksp and Kf

Determine the solubility of a compound
 Example 3.17: Will it Precipitate?
When 60.00 mL of 0.010 M Ca(NO3)2 are mixed with 40.0 mL of
0.025 M K2CrO4. (Ksp for CaCrO4 is 1 × 10−8)
Will a CaCrO4 will precipitate form?

Perform calculations involving Ksp and Kf

 Homework Example 3.18: The Precipitation Race
A solution has [Ca2+] = 0.001 M and [Ag+] = 0.001 M. Solid Na2CO3
is slowly added to the solution (assume no volume change)
CaCO3 Ksp = 3 × 10−9 Ag2CO3 Ksp = 9 × 10−12

1. Which of the two ions will ppt first?

2. What concentration of the first cation remains in solution when

the second cation starts to ppt?

3. Is CO32− an effective anion to use to separate Ca2+ and Ag+?

Perform calculations involving Ksp and Kf

Determine whether ions can be separated by precipitation