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Calculating dG Under Nonstandard State Conditions

Jul 6, 2025

Overview

This lecture explains the real-world applicability of Gibbs Free Energy (ΔG), focusing on how to calculate and interpret ΔG under non-standard conditions, using evaporation and a chemical reaction example.

Applicability of ΔG

  • Standard ΔG calculations assume standard conditions (25°C, 1 atm, 1 M concentrations).
  • Real-life scenarios often differ from standard state conditions, affecting the spontaneity of processes.
  • Example: Calculated ΔG for water evaporation at standard conditions is +8.59 kJ/mol (non-spontaneous), but water does evaporate in reality due to lower than 1 atm partial pressure.

Calculating ΔG at Non-Standard State Conditions

  • Use the equation: ΔG = ΔG° + RT ln Q, where Q is the reaction quotient.
  • R (ideal gas constant) = 8.314 J/mol·K (or 8.314 × 10⁻³ kJ/mol·K for consistency with ΔG in kJ).
  • Q represents the ratio of products to reactants, using concentrations or partial pressures (not at equilibrium).
  • For partial pressure calculations, standard state means 1 atm for gases.

Example—NO Reaction Calculation

  • Given: ΔG° = –71.2 kJ, T = 298 K, Q calculated using provided partial pressures.
  • Q = (P(NO₂))² / [(P(NO))² × P(O₂)].
  • Plug values into the ΔG equation to find ΔG under non-standard conditions.
  • Result: ΔG = –50.7 kJ, less negative than standard, meaning less spontaneous.

Interpreting Spontaneity and Work

  • Negative ΔG indicates a spontaneous reaction.
  • The more negative ΔG is, the more spontaneous the process, and the more work can be extracted.
  • A less negative ΔG under non-standard conditions means the system can do less work.

Key Terms & Definitions

  • ΔG (Gibbs Free Energy Change) — energy available to do work at constant temperature and pressure.
  • Standard State Conditions — 25°C, 1 atm pressure, 1 M concentration.
  • Reaction Quotient (Q) — ratio of product/reactant concentrations or partial pressures, not at equilibrium.
  • ΔG° (Standard Gibbs Free Energy Change) — ΔG calculated at standard state conditions.
  • R (Ideal Gas Constant) — 8.314 J/mol·K or 0.008314 kJ/mol·K.

Action Items / Next Steps

  • Practice calculating ΔG under non-standard conditions using the ΔG = ΔG° + RT ln Q equation.
  • Review definitions and units for ΔG, R, Q, and standard state conditions.
  • Prepare for problems involving real-world conditions, not just standard state scenarios.