Physical Chemistry II

(CHE21M5)

Chemical Equilibrium
Elements of Physical Chemistry, Chapter 7, from page 153
Atkin’s Physical Chemistry, Chapter 6, From page 204
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)

Equilibrium Constant, K Description Gibbs Free Energy, ∆𝐺

K>1 Product is favoured ∆𝐺 < 0 (negative)
K=1 Reaction at equilibrium. Neither reactants ∆𝐺 = 0
nor products are favoured
K<1 Reactants favoured ∆𝐺 > 0 (positive)
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Chemical Equilibrium:
Standard Conditions, ∆𝑮°
Chemical Reaction: aA + bB ↔ cC + dD
[𝐶]𝑐𝑒𝑞 [𝐷]𝑑𝑒𝑞
𝐾𝑒𝑞 =
[𝐴]𝑎𝑒𝑞 [𝐵]𝑏𝑒𝑞
[𝑐]𝑐 [𝐷]𝑑
• 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑄𝑢𝑜𝑡𝑖𝑒𝑛𝑡: 𝑄 = (not at equilibrium)
[𝐴]𝑎 [𝐵]𝑏

∆𝐺° at standard conditions (298K and 1 atm)

∆𝑮°(𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏) = σ ∆𝑮°(𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔) − σ ∆𝑮°(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)
= c ∆𝐺° (C) + d ∆𝐺° (D) – [a ∆𝐺° (A) + b ∆𝐺° (B) ]
 Relating ∆𝐺° to the Equilibrium constant
∆𝑮° = −𝑹𝑻𝒍𝒏𝑲𝒆𝒒

• The free energy change (∆𝐺)when reactants are in a non-standard state (any other state except at
1 atm or 1M) is related to the standard free energy change, ∆𝐺°, by the following equation:

∆𝐺 = ∆𝐺° + 𝑅𝑇𝑙𝑛𝑄
[𝑐]𝑐 [𝐷]𝑑
∆𝐺 = ∆𝐺° + 𝑅𝑇𝑙𝑛
[𝐴]𝑎 [𝐵]𝑏
∆𝐺 represents an instantaneous change in free energy at some point in the equation approaching
equilibrium
• 𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑐𝑜𝑛𝑑𝑖𝑡𝑖𝑜𝑛𝑠: ∆𝐺 = 0 and Q = 𝐾𝑒𝑞

−∆𝐺°ൗ )
• 𝐾𝑒𝑞 = 𝑒 ( 𝑅𝑇

• ∆𝐺° = 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝐺𝑖𝑏𝑏𝑠 𝑓𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦

• R = universal gas constant (8,314 JK-1mol-1)
• ln K = natural log of K
Exercise Questions
• The equilibrium constant for the reaction I2(g) → 2 I(g) is 0.26 at 1000 K.
What is the corresponding value of Kc at 298 K?
• The equilibrium constant K = 0.36 for the reaction PCl5(g)  PCl3(g) + Cl2
(g) at 400 K.
a). Calculate ∆G°
b). Calculate K at 298 K
c). Given that 1.5 g of PCl5 was initially placed in a reaction vessel of
volume 250 cm3, determine the molar concentrations in the mixture at
equilibrium.