Chapter 4: Chemical equilibrium | Miss Rola Fawaz

Chapter 4: Chemical equilibrium

Introduction:
Some reactions are complete, while others are incomplete.

Complete reactions:
At the end of the reaction, the reactants apply stoichiometry it means at least one of the reactants consumed totally.
Case 1: Both reactants are limiting
H2 + Cl2 → 2 HCl x: nb of moles of H2 reacted at t
Initial state (n0) nH2 initial nCl2 initial 0
∆n (reacted, formed) -x -x 2x
End of rxn 0 0 n max
𝑛 𝐻2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑛𝐶𝑙2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑛 𝐻𝐶𝑙 𝑓𝑜𝑟𝑚𝑒𝑑
A.T.S: = =
1 1 2

Case 2: One of the reactants is the limiting reactant

H2(g) + Cl2(g) → 2 HCl(g)

Initial state (mol): a b 0 where x is the
number of
moles of H2 consumed
at instant t
Change in reaction: -x -x 2x
∆n (mol)
At any instant t
(reacted, formed)

At any instant t2 a-x b-x 2x

(remained, formed)

At end of reaction (mol): 0 b-a 2a (If H2 is the limiting

t∞ reactant)

𝑛 𝐻2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑛𝐶𝑙2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑛 𝐻𝐶𝑙 𝑓𝑜𝑟𝑚𝑒𝑑 𝑛 𝐻2 𝑖𝑛𝑖𝑡𝑖𝑎𝑙

At end of the reaction (t∞): A.T.S: 1
= 1
= 2
= 1
=a

Incomplete reaction:
- Reactants don’t get completely consumed (doesn’t end).
- Constant composition at time t = teq
- Rate of formation = Rate of disappearance. At equilibrium
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 Chapter 4: Chemical equilibrium | Miss Rola Fawaz

Ex:

N2(g) + 3H2(g) ⃗⃗⃗

← 2NH3(g)
Initial state (mol): a b 0 where x is the
number of
moles of N2 consumed
at equilibrium
Change in reaction: -x -3x 2x
∆n (mol)
(reacted, formed)

At equilibrium a-x b-3x 2x

(remained, formed)

≠0 ≠0 ≠ 𝑛 𝑚𝑎𝑥

(1)

⃗⃗⃗
aA+bB← cC+dD (1): Forward
(2) (2): Backward

We have two types of equilibrium:

Gas-Gas
Homogeneous
Liquid-Liquid
Equilibrium
Gas-Liquid
Heterogeneous
Gas-Solid

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 Chapter 4: Chemical equilibrium | Miss Rola Fawaz

A- Homogeneous Equilibrium:
It is an equilibrium in which its constituents (reactants, products) are in a single phase.
1- Gas-Gas:
⃗⃗⃗
n A(g) + m B(g) ← p C(g) + q D(g)
The equilibrium constant relative to concentration is KC, where KC is calculated as the following:
𝑝 𝑞
[𝐶]𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 [𝐷]𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
KC = ; where the concentrations are at equilibrium
[𝐴]𝑛 𝑚
𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 [𝐵]𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
⃗⃗⃗ 2NH3 (g)
3H2 (g) + N2 (g) ←
Rcts , pdts are gases then homogeneous equilibrium

[𝑁𝐻3 ]2
Expression of Kc =
[𝑁2 ][𝐻2 ]3
2 NH3(g) ←
⃗⃗⃗ 3H2(g) + N2(g)

[𝑁2 ][𝐻2 ]3
Kc’ =
[𝑁𝐻3 ]2
[𝑁𝐻3 ]2 [𝑁2 ][𝐻2 ]3
Kc x Kc’ = [𝑁2 ][𝐻2 ]3
x =1
[𝑁𝐻3 ]2

Kc = 1/Kc’

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 Chapter 4: Chemical equilibrium | Miss Rola Fawaz

Note:

Kc depends on Temperature.
T varies then Kc varies

The variable factor x could be n, [ ], P

x is not selected by hypothesis, we consider x relatively for reactants, or products which has the
most simple coefficient which means 1.

Example 1:
⃗⃗⃗ PCl3 (g) + Cl2 (g)
PCl5 (g) ← X: n PCl5 consumed at equilibrium or n PCl3 formed at
I.S (mol) n0 0 0 equilibrium or n Cl2 formed at equilibrium

(since lowest coeff is 1)

∆n -x +x +x
n←⃗⃗⃗ n0 – x x x
≠0 ≠ 𝑛 𝑚𝑎𝑥 ≠ 𝑛 𝑚𝑎𝑥
𝑛0 – x 𝑥 𝑥
[ ] ←⃗⃗⃗ 𝑉 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑉𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑉𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑛 𝑎𝑡 𝑒𝑞 0 𝑛 –x
[PCl5] = 𝑉 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑉 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑛 𝑎𝑡 𝑒𝑞 x
[PCl3] = 𝑉 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑉 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑛 𝑎𝑡 𝑒𝑞 x
[Cl2] = 𝑉 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑉 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑥 𝑥 𝑥2 𝑥2
[PCl3 ][Cl2 ] )( )
𝑉 𝑉 𝑉2 𝑉
KC = = 𝑛0 −𝑥 = 𝑛0 −𝑥 = ; Calculate Kc in terms of X, n0 , V solution
[PCl5 ] 𝑛0 −𝑥
𝑉 𝑉

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 Chapter 4: Chemical equilibrium | Miss Rola Fawaz

Example 2:
⃗⃗⃗ 2NO (g) + Br2 (g)
2NOBr (g) ←
I.S (mol) n0 0 0 X: n Br2 formed at equilibrium (since
lowest coeff is 1)
∆n -2x +2x +x
n←⃗⃗⃗ n0 – 2x 2x x
𝑛← 𝑛0 – 2x 2𝑥 𝑥
[ ] ←⃗⃗⃗ = 𝑉⃗ 𝑉 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑉𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑉𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

2𝑥 𝑥
[𝑁𝑂]2 [Br2 ] ( )2 ( )
𝑉 𝑉
KC = = 𝑛 −2𝑥 2
[𝑁𝑂𝐵𝑟]2 ( 0 )
𝑉

Degree of conversion (dissociation) α:

It is the ratio between the amount reacted and the initial amount in moles.
|𝑛 𝑟𝑒𝑎𝑐𝑡𝑒𝑑|
α= ; 0<α<1
𝑛 𝑖𝑛𝑖𝑡𝑖𝑎𝑙

no rxn rxn complete

Example 3:
⃗⃗⃗ SO2 (g) + Cl2 (g)
SO2Cl2 (g) ← X: nSO2Cl2 consumed at equilibrium, or nSO2 formed at
I.S (mol) n0 0 0 equilibrium, or nCl2 formed at equilibrium

(Since lowest coeff is 1)

∆n -x +x +x
n←⃗⃗⃗ n0 – x +x +x

n←⃗⃗⃗ in terms of α n0 - α n0 α n0 α n0
[ ] ←⃗⃗⃗ n0 – x/ V x/V x/V
1. Establish a relation between α (the degree of dissociation of SO2Cl2) and x, and then complete
the table of conversion.
|𝑛 𝑟𝑒𝑎𝑐𝑡𝑒𝑑| |−𝑥| 𝑥
α SO2Cl2 = = =
𝑛 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑛0 𝑛0
x = α n0
2. Give the expression of Kc of this equilibrium.
⃗⃗⃗ SO2 (g) + Cl2 (g)
SO2Cl2 (g) ←
[𝑆𝑂 ][𝐶𝑙2 ]
Kc = [ 𝑆𝑂2
2 𝐶𝑙2 ]
𝑥 𝑥 𝑥2
[𝑆𝑂2 ][𝐶𝑙2 ] ( )( )
𝑉 𝑉 𝑉
3. Find Kc in terms of n0, x,Vsolution. Kc = [ 𝑆𝑂 = 𝑛0−𝑥 =
2 𝐶𝑙2 ] ( ) (𝑛𝑜−𝑥)
𝑉

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 Chapter 4: Chemical equilibrium | Miss Rola Fawaz

Example 4:
⃗⃗⃗ CO (g) + Cl2 (g)
COCl2 (g) ←
X: [COCl2 ]consumed at equilibrium, or [CO] formed
I.S (mol/L) C0 0 0 at equilibrium, or [Cl2]formed at equilibrium
∆[ ] -x +x +x (since lowest coeff is 1)
[ ] ←⃗⃗⃗ C0 – x x x
1. Give the expression of α (the degree of dissociation of COCl2).
𝑛 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
|𝑛 𝑟𝑒𝑎𝑐𝑡𝑒𝑑| 𝐶 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
α COCl2 = ; V is constant we multiple by 1/V= 𝑉
𝑛0 =
𝑛 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝐶0
𝑉
2. Find α in terms of C0 , and x.
𝐶 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑥
α COCl2 = =
𝐶0 𝐶0

Degree of conversion of each reactant:

N2(g) + 3H2(g) ⃗⃗⃗
← 2NH3(g)
Initial state (mol): a b 0 where x is the number of
Change in reaction: -x -3x 2x moles of N2 consumed at
∆n (mol) equilibrium
(reacted, formed)
At equilibrium a-x b-3x 2x at equilibrium
(remained, formed)

𝑥
For N2: α1 = 𝑎
3𝑥
For H2: α2 = 𝑏

2- Liquid- Liquid:
⃗⃗⃗
n A(L) + m B(L) ← p C(L) + q D(L)
The equilibrium constant relative to concentration is KC , where KC is calculated as the following:
𝑝 𝑞
[𝐶]𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 [𝐷]𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
KC = ;
[𝐴]𝑛 𝑚
𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 [𝐵]𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
Where the concentrations are at equilibrium

Note: In order to determine whether the system is at equilibrium or not, we should calculate quotient Q.
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 Chapter 4: Chemical equilibrium | Miss Rola Fawaz

[𝐶]𝑝 [𝐷]𝑞
Q= ;Where the concentrations given are at any instant t which could be at equilibrium or
[𝐴]𝑛 [𝐵]𝑚

The system is at
Q = Kc
equilibrium

After Q calculation The system is

Q<Kc moving forward
sense 1
The system is not at
Q≠ 𝐾𝑐
equilibrium
The system is
Q>Kc moving Backward
sense 2

B- Heterogeneous equilibrium:
Equilibrium of a reaction, where the constituents of equilibrium are found in many states.
Note:
 Gas has Kc
 Liquid has Kc
 Solid has no Kc
1- Gas- Liquid: (only gases are expressed in Kc)
⃗⃗⃗ p C(L) + q D(g)
n A(L) + m B(g) ←
The equilibrium constant relative to concentration is KC , where KC is calculated as the following:
𝑞
[𝐷]𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
K =C ;
[𝐵]𝑚
𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
Where the concentrations are at equilibrium

2- Gas- Solid: (only gases are expressed in Kc)

⃗⃗⃗ p C(g) + q D(s)
n A(g) + m B(s) ←
The equilibrium constant relative to concentration is KC , where KC is calculated as the following:
𝑝
[𝐶]𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
K =C ;
[𝐴]𝑛
𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
Where the concentrations are measured at equilibrium

Note:
For liquids and solids:
[S] = 1 mol/l and [L] = 1 mol/l (but if all 7

system is liquid we consider [L])

 Chapter 4: Chemical equilibrium | Miss Rola Fawaz

Exercises:
1. Given the 2 equilibriums maintained at same temperature: H.W
N2(g) + 3H2(g) ⃗⃗⃗
← 2NH3(g) ; Kc1
2NH3(g) ⃗
←⃗⃗ N2(g) + 3H2(g); Kc2
Find Kc1 in terms of Kc2.
2. Given the 2 equilibriums maintained at same temperature: H.W
SO2(g) + ½ O2(g) ⃗⃗⃗
← SO3(g) ; Kc1
2SO2(g) + O2(g) ⃗⃗⃗
← 2SO3(g); Kc2
Find Kc1 in terms of Kc2.
3. In a closed bottle of volume V, we introduce “n” moles of CO (g) and “n’ ” moles of H2O(g) at
constant T. The following equilibrium is established:
CO(g) + H2O(g) ← ⃗⃗⃗ CO2(g) + H2 (g)
Let x be the number of moles of CO2 formed at equilibrium.
Find Kc in terms of x, n, n’.
4. For the equilibrium:
H2(g) + I2(g) ⃗←
⃗⃗ 2HI(g)
The equilibrium constant concentration Kc is 50.5 at T = 448◦C.
If [H2]0 = [I2]0 = 1 mol/L, what will be the [H2] ←⃗⃗⃗ , [I2] ←⃗⃗⃗ , [HI] ←⃗⃗⃗
5. Consider the equilibrium:
2 SO2(g) + O2(g) ⃗⃗⃗
← 2 SO3(g)
a. Write the expression of Kc.
b. The Kc, at a certain T, was found to be 249. An analysis of the contents of the container at
instant t holding the 3 components at the same temperature gave the following result:
[SO2 ] = 0.0149 mol/L – [O2] = 0.0449 mol/L – [SO3] = 0.269 mol/L.
Is the system at equilibrium? If not indicate in which direction is moving.
c. Find Kc’ of the following system:
2 SO3(g) ⃗⃗⃗ 2 SO2(g)
← + O2(g)
6. Assume the following amount are measured experimentally at a certain time for the system
CH3COOH (L) + C2H5OH(L) ← ⃗⃗⃗ C4H8O2 (L) + H2O(L)
n CH3COOH = 1 mol.
n C2H5OH = 3 moles.
n C4H8O2 = 0.5 moles.
n H2O = 2 moles.
a. Knowing that Kc = 4, Show that the system is not at equilibrium.
b. Deduce the system direction.
7. Consider the reaction: COCl2 (g) ← ⃗⃗⃗ CO (g) + Cl2 (g)
Given: Kc = 2.19 × 10-10
Vcontainer = 1 l
n0 = 4 mol; Let x be the amount of COCl2 reacted at equilibrium
a. Determine the number of mole of reactants and products at equilibrium.
b. Calculate the degree of conversion of COCl2
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 Chapter 4: Chemical equilibrium | Miss Rola Fawaz

8. Given the esterification reaction:

⃗⃗⃗
C2H4O2 (L) + C2H6O(L) ← C4H8O2 (L) + H2O(L)
Given: Vcontainer = 1L n0(C2H4O2) = 2 mol and n0(C2H6O) = 3 mol
Kc = 4
Let x be the amount of C2H4O2 reacted at equilibrium
a. Find Kc’ of the inverse of this reaction
b. Determine the amount of the reactants and products at eq
c. Calculate the degree of conversion of of C2H4O2 at eq.
d. Calculate the percentage yield of this reaction.
9. Consider the reaction: 2 NO (g) + Br2(g) ← ⃗⃗⃗ 2 NOBr(g)
Given: Vcontainer = 15 L
n0(NO) = 0.6 mol and n0(Br2) = 0.3 mol
at eq ntotal = 0.85 mol
Let x be the amount of Br2 reacted at equilibrium
a. Fill the table below in terms of x

2 NO (g) + Br2(g) ⃗⃗⃗

← 2 NOBr(g)
n At t= 0
change ( ∆n) at eq
n At eq (end of rxn)

b. Determine the amount of the reactants and products at eq.

c. Calculate the value of the equilibrium constant
d. Calculate the degree of conversion of Br2

10. Consider the reaction: 2 NO (g) ⃗⃗⃗

+ Cl2(g) ← 2 NOCl(g)
Given: Vcontainer = 4 l
n0(NO) = 5mol and n0(Cl2) = 2 mol, the equilibrium is established when 0.8 mol of NOCl are formed
a. Determine the number of mole of reactants and products at equilibrium.
b. Calculate the equilibrium constant of this reaction.
c. Determine the value of Kc of the reaction below:
NO (g) + ½ Cl2(g) ←⃗⃗⃗ NOCl(g)
11. ) n mol of N2 and 3n mol of H2 are mixed at T = 127℃ to reach their equilibrium state.
Let x be the number of moles of N2 reacted at equilibrium and α be degree of conversion N2 at
equilibrium. N2(g) + 3H2(g) ↔ 2NH3(g)
1. Write the expression of α(N2).
2. Rewrite and complete the following table: ( coeff system , indicated parts in table)
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 Chapter 4: Chemical equilibrium | Miss Rola Fawaz

N2 H2 NH3

Initial state n 3n 0
Equilibrium state in terms of x
Equilibrium state in terms of α
3. Deduce a relation that allows us to calculate the total number of moles (n total) of the gases in the
equilibrium mixture in terms of n and α.
4. Number of moles of NH3 formed (n (NH3)eq ) equals 8 times the number of moles of N2 remained
(n(N2)eq). Find the value of α.
5. Determine the composition of the system in terms of n at eq if 25 % of N2 is reacted
Exercise 12: Chemical Equilibrium
2 moles of nitrogen gas (N2) and n mol of Hydrogen gas H2 are introduced initially into a closed container
of volume V = 1L at T = 127oC. The following system reaches equilibrium according to the equation:
⃗⃗⃗ 2 NH3 (g)
N2 (g) + 3 H2 (g) ←
At equilibrium, the number of moles of ammonia (NH3) formed is shown in the curve below:
1. Equilibrium state: n NH3 (mol)
1.1.Define dynamic equilibrium. 0.9

1.2.Prove according to the graph that the reaction 0.8

is slow. 0.7
1.3.Calculate the mole composition of all components 0.6
at equilibrium; knowing that the number of moles 0.5
of H2 remained is double that of N2 remained. 0.4
1.4.Determine the equilibrium constant Kc of the 0.3
above reaction. 0.2
1.5.Calculate the % yield for the production of 0.1
ammonia. 0 Time
0 50 100 150 (hour)
2. Proving a relation in terms of α:
In another experiment, n moles of N2 and 3n moles of H2 are mixed together at the same
temperature to reach their equilibrium state.
Let x be the number of moles of N2 reacted at equilibrium and α be the degree of conversion of N2
at equilibrium.
2.1.Write the expression of α.
2.2.Copy and complete the following table:
N2 H2 NH3
Initial State (mol)
Equilibrium state in terms of x
Equilibrium state in terms of α
2.3.Deduce a relation that allows us to calculate the total number of moles of gases (ntotal) in the
equilibrium mixture in terms of n and α.

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