Unit 7: Equilibrium, Khan Academy Part 1

I. Introduction to Equilibrium

Dynamic Equilibrium:
- Reversible Reactions: reactions that can go back to their original state (reverse)
and keep reacting.
- I.e. gas turning into liquid and back to a gas -> H2O (l) -> H2O (g)
<-

- Reaction reaches equilibrium when the number of molecules for the reactants
and the products remains constant.
- Equilibrium: the rate of the forward reaction is equal to the rate of the reverse
reaction.

Direction of Reversible Reactions:

- X2 (g)-> 2X (g)
<-
- Rate of forward and reverse reactions: R = Kf [X2]^1 R = Kr [X]^2
(if the concentration of X2 decreases the rate of the forward reaction also
decreases, if the concentration of X increases the rate of the reverse reaction
increases)

Rate of forward reaction is greater than rate Net conversion of reactants to products
of reverse reaction

Rate of forward reaction is equal to rate of At equilibrium, no net change

reverse reaction

Rate of reverse reaction is greater than rate Net conversion of products to reactants
of forward reaction
 II. Equilibrium Constant and Reaction Quotient
Writing Equilibrium Constant and Reaction Quotient Expressions:
- aA + bB -> <- cC + dD
- Kc = [C]^c [D]^d / [A]^a [B]^b

Example: N2 (g) + 3H2 (g) -> <- 2NH3 (g)

-Kc = [NH3]^2 / [N2] [H2]^3

- Equilibrium Constant K (partial pressure): Kp = (PC)^c (PD)^d / (PA)^a (PB)^b

- Homogeneous Equilibrium: substances in equilibrium are in the same phase.
- Heterogeneous Equilibrium: substances in equilibrium are in different phases.
- ^^ pure solids and liquids are left out when writing an equilibrium expression because the
concentration of a pure solid/liquid remains constant over time.
- Q = reaction quotient

concentration: Qc = [C]^c [D]^d / [A]^a [B]^b

partial pressure:

If Qc = Kc -> at equilibrium
If Qc > Kc (reactants favored over products) or Qc < Kc -> not at equilibrium

III. Calculating Equilibrium Constants

****************************

IV. Magnitude of the Equilibrium Constant:

Magnitude of the Equilibrium Constant (vid):

Ex 1:
- A(g) -> <- B(g)
- Kc = [B]/[A] = 0.5/0.5 = 1

Ex 2:
- A(g) -> <- B(g)
- Kc = [B]/[A] =1/10 = 0.1 K< 1 (more reactants than products at equilibrium)

Ex 3:
- A(g) -> <- B(g)
- Kc = [B]/[A] = 10/1 = 10 K> 1 (more products than reactants at equilibrium)

Properties of the Equilibrium Constant:

- To find the reverse reaction of the original equilibrium constant take its inverse (1/Kc
value)
- When multiplying the equation by X, raise the equilibrium constant by X (i.e. multiply by
2, raise by a power of 2)
Example:

V. Calculating Equilibrium Concentrations

Calculating an Equilibrium Constant from Initial and Equilibrium Pressures:

I -> Initial Partial Pressure

C -> Change in Partial Pressure
E -> Equilibrium in Partial Pressure

Example: PCl5 (g) -> <- PCl3 (g) + Cl2 (g) at 500K
I -> 1.66 atm , 0 (for PCl3 & Cl2)
C -> -x (for PCl5) , x (for PCl3 & Cl2)
E -> 1.66 -x , 0 + x (for PCl3 & Cl2)

Dalton's Law: Ptotal = PCl5 + PCl3 + Cl2

2.35 = 1.66 -x + x + x
0.69 = x
1.66 - 0.69 = 0.97

Kp = (PpCl3) (pCl2) / PpCl5 = 0.69^2 /0.97 = 0.49 atm

Calculating Equilibrium Concentrations from Initial Concentrations:

Example: Br2 + Cl2 -><- 2BrCl

I (M) 0.60 + 0.60 0

C (M) -x -x 2x
E (M) 0.60 - x 2x
Kc = [BrCl]^2 / [Br2] [ Cl2]
7.0 = 2x^2 / (0.60 - x) (0.60 - x)
7.0 = 2x^2 / (0.60 -x)^2
2 2
7. 0 = 2𝑥 / (0. 60 − 𝑥)
1.59 = 4.65x
x = 0.34

0.60-.034 = 0.26 M
2(0.34) = 0.68 M

VI. Using the Reaction Quotient

Using the Reaction Quotient (video):
- Example: A (g)-><- B K = 3 at 25 ° C

1st particulate diagram: Qc = [B]/[A] = .3/.5 = 0.6

- Qc (0.6) < Kc (3) -> reaction is not at equilibrium
^^ too many reactants, not enough products

2nd particulate diagram: Qc = 0.5/0.3

- Qc (1.666) < Kc (3)

3rd particulate diagram: Qc = .6/.2 = 3

- Qc = Kc -> at equilibrium

Too many reactants, not

enough products

Too many products, not

enough reactants.

At equilibrium
Worked Example: Using the reaction quotient to find equilibrium partial pressures

Worked Example: Using the reaction quotient to predict a pressure change

VII. Le Chatelier’s Principle

Le Chatelier’s Principle: Changing Concentration

“If a stress is a applied to a reaction mixture at equilibrium the net reaction goes in the direction
that relieves the stress”

Example: A(g) -><- B(g) K = 3 at 25 °C

(If A increases the net reaction will go to the right to decrease the concentration of A)

1st particulate diagram:

Qc = [B]/[A] .3/.1 = 3
Qc = Kc (at equilibrium)

2nd particulate diagram:

Qc = .3/.5 = .6
Qc < Kc

3rd particulate diagram:

Qc = .6/.2 = 3
Qc = Kc (equilibrium has been re-established)

<- Le Chatelier's Principle

Graph example

Le Chatelier’s Principle: Changing Volume

A(s) -> B (s) + C(g) Kc = 0.4 at 25°C

Observations:
 - Volume Decreases so pressure increases
- Reaction will move towards the reactants to relieve pressure caused by gas.
- ^^ it will increase the solid A and decrease the gas C

Qc = [C]
[C] = 0.4 / 1.0 = 0.4 M
0.4/0.5 = 0.8 M
0.2/0.5 = 0.4

First diagram (V= 1.0L): Qc = 0.4 , Qc = Kc

Second Diagram (V = 0.5L): Qc = 0.8 , Qc > Kc
Third Diagram (V = 0.5L): Qc = 0.4 , Qc = Kc

- Changing the volume when there are equal amounts of moles on both sides will not
change the reaction.
- Adding an inert gas (gas that does not react with other substances) to the equation does
not change the composition of the reaction.

Le Chatelier’s Principle: Changing Temperature

- When you increase the temperature, the value for the equilibrium constant (Kc) will
decrease (during exothermic reaction). Qc > Kc A←----B
- When you decrease the temperature, the value for the equilibrium constant
increases (Kc) (during an exothermic reaction). Qc < Kc A----> B
- Catalyst: Speeds u p the forward and reverse reactions (rates are still equal aka no
change in the composition of the equilibrium mixture).

Worked Example: Calculating the equilibrium total pressure after a change in volume:
Worked Example: Using Le Chatelier’s Principle to predict shifts in equilibrium

VIII. Solubility Equilibria

Introduction to Solubility Equilibria

BaSO4 (s) -><- Ba2+ (aq) + So42- (aq)

Ksp = [Ba2+] [So42-]
−10
Ksp = 1.1x10 at 25°C
- If Ksp > 1 the substance is a soluble salt (i.e. NaCl)
- The solubility of a substance refers to the amount of solid that dissolves to form a
saturated solution (units for solubility g/L).
- Molar Solubility refers to the number of moles of the solid that dissolve to form 1 Liter of
the saturated solution (units: mol/L or M)
- The higher the Ksp value the more soluble the salt.
- The higher the value of Ksp of a chemical compound, the higher the concentration of its
ions at equilibrium.
Worked Example: Calculating solubility from Ksp

Worked Example: Predicting whether a precipitate forms by comparing Q and Ksp

The Common-Ion Effect:

- The common-ion effect refers to the decrease in solubility of an ionic precipitate by the
addition to the solution of a soluble compound with an ion in common with the
precipitate. This behavior is a consequence of Le Chatelier's principle for the equilibrium
reaction of the ionic association/dissociation.

PbCl2(s) -><- Pb2+(aq) + 2Cl- (aq)

- The common ion effect says that the solubility of a slightly soluble salt (i.e. Pb2+) is
decreased by the presence of a common ion (i.e. Cl-)

pH and Solubility:

Example: PbF2(s) -><- Pb2+ 2F-

- Decreasing the pH (or making the solution more acidic) will ause the reaction to flow to
the right (less PbF2)