– CHEMICAL EQUILIBRIUM –

Week 5: Modules 13-14

Chapter 14
Practice Problems: 14.23, 14.25, 14.35, 14.37, 14.39, 14.41,
14.43, 14.51, 14.53, 14.55, 14.57, 14.59, 14.61, 14.63, 14.73,
14.75, 14.83, 14.87, 14.121, 14.123.

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 – CHEMICAL EQUILIBRIUM –
MODULE 13
1. INTRODUCTION

a. Non-Reversible Reactions

Let us consider the reaction that we saw earlier (Chemical Reactions Notes p10, Question 3)

2 HCl(aq) + Ba(OH)2(aq) → Ba(Cl)2(aq) + 2 H2O(l)

The PRODUCTS of the reaction: Ba(Cl)2 and H2O, CANNOT react together to give us back HCl and
Ba(OH)2. The reaction is NON-REVERSIBLE, it only proceeds in the FORWARD DIRECTION: we used

the arrow → to indicate the direction in which the reaction did proceed: from reagents to products.
Indeed, all of the reactions that we have looked at and done calculations for based on the stoichiometry had
that in common they were all non-reversible Even if the yield was not 100% (i.e. the reaction did not quite
reach completion), the products formed could NEVER react together in the backward reaction to give the
reagents.

b. Reversible Reactions

Some reactions can proceed in both the FORWARD direction and the BACKWARD direction. That is to
say that Reagents can react together to give Products and Products can react together to give Reagents.

These reactions are said to be REVERSIBLE and to indicate this we use the arrow ⇌.

Example: CO(g) + 3 H2(g) ⇌ CH4(g) + H2O(g) in a closed vessel.

 If we mix PURE CO and H2 the reaction will proceed in the forward direction until we reach
EQUILIBRIUM
 If we mix PURE CH4 with H2O, the reaction will proceed in the backward or reverse direction
until we reach EQUILIBRIUM.
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c. AT EQUILIBRIUM (Sect 14.1)

When we reach EQUILIBRIUM, or as we say at “CHEMICAL EQUILIBRIUM”, the

Rate of FORWARD reaction = Rate of REVERSE reaction .

This means that we now have a DYNAMIC SYSTEM where there is constant movement in the forward and
backward direction but there is no overall change in the amount of reactants or products, i.e.,

CaCO3(s) ⇌ CaO(s) + CO2(g) (enclosed sealed vessel) Dissociation

H2O(l) ⇌ H2O(g) (sealed bottle) Vaporization
Ag+(aq) + Cl–(aq) ⇌ AgCl(s) Solubilization

2. EQUILIBRIUM CONSTANTS (14.2)

Let’s take the association of NO2 as an example:
2 NO2(g) ⇌ N2O4(g)

Rate of Association

Rate of Dissociation

EQUILIBRIUM IS REACHED HERE!

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  Once we have reached Equilibrium the rate of ASSOCIATION is equal to the rate of
DISSOCIATION

Rate of Association = kA [NO2]2

kA [NO2]2 = kD [N2O4]
Rate of Dissociation = kD [N2O4]

 Once we have reached equilibrium, the concentrations of the products and reagents remain constant

Thus we find that based on concentrations

[N2O4] kA
= = Constant at a given Temperature (T)
[NO2]2 kD
Because all species are in the same gaseous state we can also write
P{N2O4}
= Constant at a given Temperature (T)
P{NO2}2

The constants are called Equilibrium Constants K

[N2O4]
Kc = = Constant at a given Temperature (T)
[NO2]2
P{N2O4}
Kp = = Constant at a given Temperature (T)
P{NO2}2

a. General Form for Equilibrium Constant

The value of the equilibrium constant expression is constant for a particular reaction at a given temperature,
whatever equilibrium concentrations (or pressures) are substituted - this is known as the “Law of Mass
Action

For an equilibrium of the form:

a A(aq) + b B(aq) ⇌ c C(aq) + d D(aq)

[C]c × [D]d
Kc =
[A]a × [B]b

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For an equilibrium of the form:

a A(g) + b B(g) ⇌ c C(g) + d D(g)

PC c × P D d
KP =
PA a × P B b

Key Points on Equilibrium constants:

 If concentrations in unit [moles L-1] are used the equilibrium expression is given as KC
 If Partial Pressures in unit atm are used the equilibrium expression is given as KP
 We always write Products / Reagents and the powers in the K expression are determined by the
reaction coefficients of the reactants and products in the chemical equation
 If any of the species in in the equilibrium reaction is heterogeneous, e.g. solid (s) or liquid (l), their
concentrations do not affect the equilibrium and do not appear in the equilibrium constant K.
 External factors such as Volume, Pressure, concentrations will affect the equilibrium but not the K
value. Their effect can be predicted using Le Chatelier’s Principle (see below)
 Temperature is the ONLY EXTERNAL factor that will affect the value of the Equilibrium constant
K.

Example of variation of K with T:

Temperature (Kelvin) KC
H2(g) + Cl2(g) ⇌ HCl(g)
300 4 × 1031
500 4 × 1018
1000 5.1 × 108

 Pure Solids do not enter into the Equilibrium Constants (14.3)

CaCO3(s) ⇌ CaO(s) + CO2(g)

KP = PCO2 and KC = [CO2]

 Pure Liquids do not enter into the Equilibrium Constant (14.3)

CH3COOH(aq) + H2O(l) ⇌ H3O+(aq) + CH3COO–(aq)

[CH3COO–] × [H3O+]
Kc =
[CH3COOH]

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b. Direction and Extent of an Equilibrium (14.4)

The value of K the equilibrium constant indicates what side of the equilibrium is favoured and to what extent.
(i) 2 NO (g) + O2(g) ⇌ 2 NO2(g) [NO2]2
Kc = = 1.6 × 1012
[NO]2 × [O2]
KC >> 1 and is a very large number the Products
are Heavily Favoured, the equilibrium lies to the right side.

N2O4 (g) ⇌ 2 NO2(g) [NO2]2

Kc = = 0.21
[N2O4]
KC < 1 Reagent is favoured: the equilibrium lies to the left side. If KC was 2.1 × 10-5 then we would say that
the reagent is Heavily Favoured and that the equilibrium lies largely to the left.

c. K values for Reverse Reaction

If we REVERSE an equation, INVERT K.

(i) 2 NO (g) + O2(g) ⇌ 2 NO2(g) [NO2]2

Kc(i) = = 1.6 × 1012
[NO]2 × [O2]

(ii) 2 NO2(g) ⇌ 2 NO(g) + O2(g)

[NO]2 × [O2] 1
Kc(ii) = = = 0.62 × 10-12
2
[NO2] Kc(i)
-1
We may also write KC(ii) = KC(i)

d. K values multiples or fraction of reactions reaction

[NO2]2
(i) N2O4 (g) ⇌ 2 NO2(g) KC(i) =
[N2O4]
2
[NO2]4 = [NO2]2
(ii) 2N2O4 (g) ⇌ 4 NO2(g) KC(ii) = = KC(i)2
[N2O4]2 [N2O4]

If we double a reaction Knew = (Korig)2

If we triple a reaction Knew = (Korig)3
If we half a reaction Knew = (Korig)1/2 = √Korig
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e. K values of a reaction resulting from adding reactions
[NO]2[O2]
Find the value of KC for this reaction N2O4 (g) ⇌ 2 NO(g) + O2(g) KC =
[N2O4]

[NO2]2
We know (i) N2O4 (g) ⇌ 2 NO2(g) KC(i) = = 0.26
[N2O4]

(ii) 2 NO2 (g) ⇌ 2 NO(g) + O2(g) [NO]2[O2]

KC(ii) = = 6.3 10-13
2
[NO2]

Adding (i) and (ii) N2O4 (g) ⇌ 2 NO(g) + O2(g) Multiply KC(i) and KC(ii)

[NO2]2 [NO]2[O2] [NO]2[O2]

KC(i) x KC(ii) = x = = KC = 0.26 x 6.3 10-13 = 1.3 10-13
2
[N2O4] [NO2] [N2O4]
When adding two or more equations: Knew = Ka x Kb x Kc ….

END OF MODULE 13
Please complete activity 13

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 – CHEMICAL EQUILIBRIUM –
MODULE 14
3. QUANTITATIVE CALCULATIONS (14.5)
We need to be able to predict if
1. we are at Equilibrium
2. if the reaction is moving left to right
3. it the reaction is moving right to left

To do that we look at the “reaction quotient” Q which is calculated using the expression of the equilibrium
constant with the experimental concentrations at a given time t. We compare this calculated experimental Q
to the value for K

1. If Q = K , then we’re at equilibrium.

2. If Q < K , then the reaction is moving L → R until Q = K, not enough products

3. If Q > K , reaction is moving L ← R until Q = K, as we have too much products

Question 2: Consider the following reaction. At 450°C, the equilibrium constant Kc = 0.159
N2(g) + 3 H2(g) ⇌ 2 NH3 (g)
If 0.683 mol of N2, 0.744 mol of H2 and 8.80 mol of NH3 are mixed in a 1.00 L container at 450°C, which
of the following is true?
A) [N2] = [H2] = [NH3] at equilibrium. B) NH3 will be formed until equilibrium is reached.
C) N2 & H2 will form until equilibrium reached. D) System
[NH3]2
Q= = is at equilibrium & no net change occurs.
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[N2] × [H2]

[Ans: Q = 275, Q is “Product Heavy” The reaction goes from Right to Left]

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 Le Chatelier’s Principle (p 611, 14.7–14.8)

Le Chatelier’s Principle states that when a system in chemical equilibrium is disturbed by a change in
temperature, pressure, or concentration, the system shifts in equilibrium composition in a way that tends to
counteract this change.

One can increase or decrease the yield of product(s) through:

1. Changing the concentration by removing or adding product(s) or reactant(s) to

the reaction vessel.

2. Changing the partial pressure of gaseous reactants and products

(i.e., through changing the volume).

3. Changing the temperature.

Question 3: Consider the equilibrium:

C(s) + CO2(g) + heat ⇌ 2 CO(g)
What is the direction of the net reaction as the new equilibrium is achieved when
(a) carbon dioxide is removed from the equilibrium mixture?

(b) the internal pressure of the reaction vessel is increased by the addition of N 2(g)?

(c) the reaction vessel is cooled?

(d) the volume of the reaction vessel is increased?

(e) more graphite is added?

[Ans: (a), R to L; (b) No Change; (c) R to L; (d) L to R; (e) No Change]

Note: Internal Pressure = PCO + PCO2, when we add N2 in (b) the Internal Pressure = PCO + PCO2 + PN2 but
PCO and PCO2 do not change!

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 4. CALCULATING EQUILIBRIUM CONCENTRATIONS (14.6)

Once we have determined the equilibrium constant for a reaction, we can use it to calculate the concentrations
of substances in an equilibrium.

Question 4: Consider the acetic acid system described by the following reaction:
CH3COOH(aq) + H2O(l) ⇌ CH3COO–(aq) + H3O+(aq) KA = 1.8 × 10–5
What is the equilibrium hydronium ion concentration, [H3O+], given the following equilibrium
concentrations: [CH3COOH] = 0.500 M & [CH3COO–] = 0.0056 M?

[CH3COO–] [H3O+] 0.0056 M × [H3O]+

KA = = = 1.8 × 10–5
[CH3COOH] 0.5000 M

1.8 × 10–5 × 0.500 M

+
[H3O] = =
0.0056 M

Question 5: Consider the reaction

PCl3(g) + Cl2(g) PCl5(g)

The equilibrium value KC equals 49.0 at 230°C.

If 4.00 mol each of phosphorous trichloride and chlorine are added to a 4.0 L reaction vessel, what is the
equilibrium composition of the mixture at 230 °C.

1. Calculate Initial Concentrations [PCl 3]initial = [Cl2]initial =

2. Write an ICE Table

PCl3(g) + Cl2(g) ⇌ PCl5(g)
Initial 1.0 M 1.0 M 0.0
Change -x -x +x
Equilibrium 1.0 M - x 1.0 M - x +x

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 [PCl5]eq +x +x
KC = = = = 49.0
[PCl3]eq [Cl2]eq (1.0 – x) (1.0 – x) (1.0 - x)2

+x
= 49.0 ∴ + x = 49.0 – 98.0x + 49.0x2
2
1.0 – 2x + x

Quadratic equation: ax2 + bx + c = 0

 b  b 2  4ac
Quadratic equation solution: x 
2a
49.0 x2 – 99.0 x + 49.0 = 0

99.0 ± √ (-99.0)2 – 4 × 49.0 × 49.0 99.0 ± 14.036

x= = =
2 × 49.0 98.0

{Ans: [PCl3] = [Cl2] = 0.13 M; [PCl5] = 0.867 M}

Question 6: Consider the following reaction:

4 PCl3(g) ⇌ P4(g) + 6 Cl2(g)

If the initial concentration of PCl3 is 1.0 M, and “x” is the equilibrium concentration of P 4, what is the correct
equilibrium relation?

4 PCl3(g) ⇌ P4(g) + 6 Cl2(g)

Initial 1.0 M 0.0 M 0.0
Change -4x +x +6x
Equilibrium 1.0 M - 4 x +x +6x

a) KC = x7/(1.0 – x)4 c) KC = (x)(6x)6/ (1.0 – 4x)4

b) KC = 6x7/(1.0 – 4x)4 d) KC = 6x7/(1.0 – x)4

{Ans c)}

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 END OF MODULE 14
Please complete activity 14

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