CHEM 1043 General Chemistry II
Tutorial 5
Review on Key Points in
Topic 5: Entropy & Gibbs Energy
Chenxi XIONG
[email protected]
1
Outlines of Topic 5
◆ Spontaneous Change: Entropy and Gibbs Energy
1. Evaluate entropy change
• Clausius’s View
• Boltzmann’s View
2. The Second Law of Thermodynamics
3. Gibbs energy
• ΔG of a system of variable composition
• Relationship between ∆rG°and K
• Gibbs energy for coupled reactions
Entropy
◆ Definition
Entropy is the yardstick to measuring the dispersal of energy
• Clausius’s View
• Boltzmann’s View
Entropy change: Clausius’ View
Entropy is related to the heat transfer.
𝛿𝑞𝑟𝑒𝑣
𝑑𝑆 =
𝑇
𝒒𝒓𝒆𝒗
∆𝑺 =
𝑻
Entropy change: Clausius’ View
◆ Constant pressure or volume
𝑇𝑓
• Constant P ∆𝑺 = C𝒑 ln Heating or cooling
𝑇𝑖
𝑇𝑓 at constant pressure
• Constant V ∆𝑺 = C𝒗 ln
𝑇𝑖
◆ Constant Temperature
𝑝𝑓
• If P changes ∆𝑺 = −𝒏𝑹 ln
𝑝𝑖
For idea gas
• If V changes
𝑉𝑓
∆𝑺 = 𝒏𝑹 ln
𝑉𝑖
𝑻𝒇 𝒑𝒇
• If the process changes from Pi, Ti to Pf, Tf ∆𝑺 = 𝑪𝒑 𝒍𝒏 − 𝒏𝑹 𝐥𝐧
𝑻𝒊 𝒑𝒊
Question1: Calculating the entropy change (Clausius’ View)
Calculate the entropy change for the following constant pressure process.
Entropy change: Boltzmann’ View
Entropy is related to the way in which the energy of a system is
distributed among the available energy levels.
• The numbers of energy levels
• The numbers of ways of arranging the particles in these energy levels
𝑆 = 𝑘𝐵 ln 𝑊
𝑺 Entropy
𝒌𝑩 Boltzmann constant = 1.3807x10-23 J·K-1
𝑾 Number of microstates
Absolute Entropy
Standard molar entropy, 𝑺°
The absolute entropy of one mole of substance in its standard state.
Question2: Calculating the standard entropy of reaction
Calculate the standard reaction entropy at 298.15 K for the conversion of nitrogen
monoxide to nitrogen dioxide (a step in the manufacture of nitric acid).
The Second Law of Thermodynamics
∆𝑺𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = ∆𝑺𝒔𝒚𝒔𝒕𝒆𝒎 + ∆𝑺𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔 > 𝟎 for spontaneity
If ∆𝑆𝑢𝑛𝑖 > 0, the process is spontaneous;
If ∆𝑆𝑢𝑛𝑖 < 0, the process is non-spontaneous;
If ∆𝑆𝑢𝑛𝑖 = 0, the process is reversible and the system has reached equilibrium;
Gibbs Energy and Gibbs Energy Change
Gibbs Energy G=H−T·S
Gibbs energy change ∆G = ∆H − T · ∆S
If∆G > 0, the process is spontaneous;
If∆G < 0, the process is non-spontaneous;
If∆G = 0, the process is reversible and the system has reached equilibrium;
Gibbs Energy change of a system of a variable composition
The change of Gibbs energy arises from changes in the amounts of substances
The standard Gibbs energy of reaction ∆𝒓 𝑮° : the Gibbs energy change per mole of
reaction for the following process.
(Standard state)
The standard Gibbs energy of formation ∆𝒇 𝑮° : the Gibbs energy change per mole
of reaction in which a substance in its standard state is formed from its elements in
their reference forms in their standard states
Gibbs Energy of Reaction for Non-standard Conditions
∆𝒓 𝑮 = ∆𝒓 𝑮° + 𝑹𝑻 𝐥𝐧 𝑸
∆𝒓 𝑮 is the Gibbs energy of reaction; Q is reaction quotient
Relationship of ∆𝒓 𝑮° to the Equilibrium Constant K
∆𝒓 𝑮 = ∆𝒓 𝑮° + 𝑹𝑻 𝐥𝐧 𝑸
At equilibrium, ∆𝒓 𝑮 = 𝟎, 𝑸 = 𝑲.
∆𝒓 𝑮° = −𝑹𝑻 𝐥𝐧 𝑲
Combine both equations,
𝑸
∆𝒓 𝑮 = 𝑹𝑻 𝐥𝐧( )
𝑲
∆𝒓 𝑮 Gibbs free energy (kJ)
∆𝒓 𝑮° Standard Gibbs free energy (kJ)
R Ideal gas constant = 8.314 J⋅K-1⋅mol-1
T Temperature (K)
K Thermodynamic equilibrium constant Thermodynamic
Q reaction quotient
K as Functions of Temperature
The relationship between K and T
∆𝐺 ° = ∆𝐻° − T · ∆𝑆 °
∆𝐺 ° = −𝑅𝑇 ln 𝐾
∆𝐺 ° ∆𝐻° ∆𝑆 °
ln 𝐾 = − =− +
𝑅𝑇 𝑅𝑇 𝑅
𝑲𝟐 ∆𝑯° 𝟏 𝟏
The Van’t Hoff equation 𝐥𝐧 =− −( − )
𝑲𝟏 𝑹 𝑻𝟐 𝑻 𝟏
Apply in determining K at different temperature
Question3: Calculating the Gibbs energy change
CHEM 1043 General Chemistry II
Tutorial 6
Review on Key Points in
Topic 5: Entropy & Gibbs Energy
Chenxi XIONG
[email protected]
