Physical Chemistry II

(CHE21M5)

Lecture #9:
Chemical Equilibrium
“The principle”
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Chemical Equilibrium
• Definition: A state in which the rates of the forward and reverse reactions are equal and the
concentrations of the reactants and products remain constant (i.e. haemoglobin has to be able to
take up oxygen, but also to release it)
• For equilibrium: at constant temperature and pressure, a reaction mixture tends to adjust its
composition until its Gibbs energy is a minimum (∆G ≈ 0).
• Also known as reversible reaction: Products can turn back into reactants automatically. Note that
equilibrium reactions are reversible but not all reversible reactions are in equilibrium.

𝐜 𝐝
𝐂 𝐃
• Equilibrium constant ratio K: aA + bB cC + dD K = 𝐚 𝐛
𝐀 𝐁

• Note: Chemical reaction MUST be balanced to obtain the correct coefficients, solids and liquids
are not included (only gases), Kc for molarity (aqueous medium) and Kp for atm, K can never be
zero or negative
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Chemical Equilibrium
• The magnitude of an equilibrium constant is a good qualitative indication of the feasibility of a
reaction regardless of whether the system is ideal or not. Expresses the composition of an
equilibrium mixture as a ratio of products of activities.
• Broadly speaking, if K >> 1, then the reaction has a strong tendency to form products.
• If K << 1 (that is, for K < 10−3), then the equilibrium composition will consist of largely unchanged
reactants.
• If K is comparable to 1 (typically lying between 10−3 and 103), then significant amounts of both
reactants and products will be present at equilibrium.
How to write K formulas for reactions: Example: N2 (g) + 3H2 (g)  2NH3 (g)
Exercise:
1. Ni (CO)4 (g)  Ni(s) + 4CO(g)
2. 3NO (g)  N2O(g) + NO2 (g)
3. CH4 (g) + 2H2S (g)  CS2(g) + 4H2(g)

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Calculations: Equilibrium Constant
Example 1: Àt equilibrium a mixture contains 0,0235 M [CO2], 0,399M [H2], 0,115 M [CO] and 0,210M
[H2O]. Calculate Kc. CO2 (g) + H2 (g) CO (g) + H2O (g)
[CO][H2O] 0,115 x 0,399
Kc = = = 0,258
[CO2][H2] 0,235 x 0,210

Example 2: Consider the following chemical reaction: C (s) + H2O (g) CO (g) + H2 (g)
A mixture of gases that results in an important industrial fuel called water gas. When equilibrium is
achieved at 800 oC, [H2] = 4x10-2M, [CO] = 4x10-2M and [H2O] = 1x10-2M. Calculate Kc at this temperature.
[CO][H2] (4x10−2)x(4x10−2)
Kc = = = 0,16
[H2O] 1x10−2

Example 3: At 900K the following reaction has Kp = 0,345: 2SO2 (g) + O2 (g) 2SO3(g) In an equilibrium mixture
the partial pressures of SO2 and O2 are 0,215 atm and 0,679 atm respectively. What is the equilibrium partial pressure
of SO3
[SO3]2
Kp = = 0,345  [SO3]2 = 0,345 x [O2][SO2]2 =
[O2][SO2]2
[SO3] = 0,345 x0,679 x 0,2152 = 0,104 atm 4
Initial Change Equilibrium Methods: ICE
Method for calculating the concentrations of all the species/components at equilibrium:

1. The initial molar concentrations of solutes or partial pressures of gases.

2. The changes in these quantities that must take place for the system to reach equilibrium.
3. The resulting equilibrium values.

• In most cases, we do not know the change that must occur for the system to reach
equilibrium, so the change in the concentration or partial pressure of one species is
written as x and the reaction stoichiometry is used to write the corresponding changes in
the other species.
• When the values at equilibrium (the last row of the table) are substituted into the
expression for the equilibrium constant, we obtain an equation for x in terms of K. This
equation can be solved for x, and hence the concentrations of all the species at
equilibrium may be found.
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Calculations: ICE method
Example 1: A mixture of 0,10 mol of NO, 0,050 mol of H2 and 0,1 mol of H2O is placed in a 1,0 L
vessel. The following equilibrium is established:
2NO (g) + 2H2 (g) N2 (g) + 2H2O (g)
At equilibrium [NO] = 0,062M. Calculate the equilibrium concentrations [H2], [N2] and [H2O]
Some H2O was
2NO (g) 2H2 (g) N2 (g) 2H2O (g) already in the
Initial 0,1 0,05 0 0,1 vessel
Change -2x = 0,038 -2x = 0,038 +x = 0,019 +2x = 0,038
Equilibrium 0,1 – 2x = 0,05 – 2x = X = 0,019 0,1 + 2x =
0,062 0,138
n 0,10
Convert mol  concentration c = = = 0,10 mol.dm-3
V 1,0 L
0,1 – 2x = 0,062 [H2] = 0,012 M
2x = 0,038 [N2] = 0,019 M
[H2O] = 0,138 M
X = 0,019
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Calculations: ICE method
Example 2: Iodine molecules react reversibly with iodide ions to produce triiodide ions.
I2(aq) + I−(aq) ⇌ I−3(aq)
If a solution with the concentrations of I2 and I− both equal to 1.000 × 10−3M before
reaction gives an equilibrium concentration of I2 of 6.61 × 10−4M, what is the equilibrium
constant for the reaction?

1 x 10-3 – x = 6,61 x 10-4

x = 1x10-3 – 6,61 x 10-4
x = 3,39 x10-4
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Calculations: I C E method
Given this equation: H2 (g) + I2 (g) 2HI(g)
Calculate all three equilibrium concentrations when [H2] = [I2] = 0,20M initially and Kc = 64,0

H2 (g) I2 (g) 2HI (g) [HI]2

Kc =
[H2][I2]
Initial 0,2 0,2 0
Change -x -x +2x [2x]2 [2x]2
64,0 = =
[0,2−x][0,2−x] [0,2−x]2
Equilibrium 0,2 – x 0,2 - x +2x
[2x]
8 = [0,2−x]

8 (0,2-x) = 2x
[H2] = [I2] = 0,2 – 0,16 = 0,04M
[HI] = 2x 0,16 = 0,32 M
16 – 8x = 2x
10x = 1,6
X = 0,16

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Calculations: I C E method

A reaction mixture initially contains 0,25M [CO] and 0,4M [O2]. At equilibrium, the concentration of
[CO2] is 0,15M. Calculate Kc.
2CO (g) O2 (g) 2 CO2 (g)
2CO (g) +O2 (g) 2 CO2 (g)
Initial 0,25 0,4 0
Change -2x -x +2x
Equilibrium 0,25 – 2x 0,4 - x 0,15 = 2x
[CO2]2 [0,15]2
Kc = = = 6,92
[CO]2[O2] [0,1]2[0,325] 2x = 0,15
X = 0,075
[CO] = 0,25-(2x0,075) = 0,1M
[O2] = 0,4-0,075 = 0,325M
[CO2] = 0,15 M

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Exercise:
1. A reaction mixture initially contains 0,75M of [HI]. At equilibrium the concentration of [I2] was found to be 0,3M.
Calculate the equilibrium concentration of [HI] in the mixture. 2HI(g) H2 (g) + I2 (g)
2. 2,0 M of I2 and 2,0 M of Br2 are initially present in a reaction mixture. Calculate the equilibrium concentration of
[I2], [Br2] and [IBr] at 425K. Given: Kc = 100. I2 (g) + Br2 (g) 2IBr(g)

3. 2,523g of H2 and 200 g of Br2 are placed in a 450 ml vessel. Calculate the equilibrium concentration of [HBr] in the
reaction vessel at 500K. Given Kc = 400. H2 (g) + Br2 (g) 2HBr(g)

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