Gibbs Free Energy from K — The Bridge Between Thermodynamics and Equilibrium
Imagine you're pushing a heavy box across a rough floor. You push hard, but the box barely moves. The potential to move is there — you're applying force — but the actual motion is tiny. That's the difference between thermodynamic spontaneity (the push) and equilibrium (where the box sits, barely budging).
Gibbs Free Energy (ΔG) tells you the push — whether a reaction can happen. The equilibrium constant K tells you how far it actually goes before stopping. The equation that links them is one of the most powerful in chemistry:
ΔG∘=−RTlnK
Let's unpack this from the ground up.
Step 1: What is ΔG?
Gibbs Free Energy change (ΔG) measures the maximum useful work a reaction can do at constant temperature and pressure. More practically:
- If ΔG<0: the reaction is spontaneous (it can happen on its own).
- If ΔG>0: the reaction is non-spontaneous (it needs energy input).
- If ΔG=0: the system is at equilibrium — no net change.
But here's the catch: ΔG depends on how much reactant and product you have at any moment. It's not a fixed number.
Step 2: Standard vs. Non-standard Conditions
Chemists define a standard state (pure substances at 1 bar, 1 M concentration for solutions, 25°C usually). Under those conditions, the free energy change is called ΔG∘ (standard Gibbs free energy change).
But real reactions rarely start at standard conditions. So we have:
ΔG=ΔG∘+RTlnQ
where Q is the reaction quotient (ratio of products to reactants at that instant, raised to their stoichiometric coefficients).
R is the gas constant (8.314 J/mol·K), T is temperature in Kelvin. The ln is natural log.
Step 3: At Equilibrium — The Key Insight
At equilibrium, the reaction has no net tendency to go forward or backward. That means:
And the reaction quotient Q becomes exactly the equilibrium constant K.
So plug into the equation:
0=ΔG∘+RTlnK
Rearrange:
ΔG∘=−RTlnK
That's it. This single equation connects a thermodynamic property (ΔG∘) with a concentration-based constant (K).
Step 4: What This Tells You
| ΔG∘ value | K value | Meaning |
|---|
| Negative (<0) | K>1 | Products favoured at equilibrium |
| Zero (=0) | K=1 | Equal amounts at equilibrium |
| Positive (>0) | K<1 | Reactants favoured at equilibrium |
A negative ΔG∘ does not mean the reaction is fast — only that it's thermodynamically favourable. Kinetics (activation energy) is a separate story.
Step 5: A Concrete Example
Consider the reaction: N2(g)+3H2(g)⇌2NH3(g)
At 25°C, ΔG∘=−33.3 kJ/mol. Using R=8.314 J/mol⋅K:
−33,300=−(8.314)(298)lnK …