Q.At 60 °C, dinitrogen tetroxide is 50 per cent dissociated. Calculate the standard free energy change at this temperature and at one atmosphere.
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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:
ΔG=0
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 …
Concept: Standard Gibbs free energy change from the equilibrium constant: ΔG∘=−RTlnKp.
Reasoning:
-
The reaction is N2O4(g)⇌2NO2(g). Let initial moles of N2O4 be 1. At 50% dissociation, moles at equilibrium: N2O4=0.5, NO2=1. Total moles =1.5.
-
Partial pressures (total pressure P=1 atm):
PN2O4=1.50.5×1=31 atm,
PNO2=1.51×1=32 atm.
-
Kp=PN2O4(PNO2)2=1/3(2/3)2=1/34/9=34. …
Find Kp from the 50% dissociation, then use ΔG⊖=−RTlnKp. With Kp=4/3 at 333 K, ΔG⊖=−796.5 J mol−1 (≈−0.80 kJ mol−1).
Set up the equilibrium
N2O4(g)⇌2NO2(g).
Start with 1 mol N2O4; degree of dissociation α=0.5:
- N2O4=1−0.5=0.5 mol
- NO2=2×0.5=1.0 mol
- total =1.5 mol
Partial pressures (total pressure =1 atm)
pN2O4=1.50.5×1=31 atm,pNO2=1.51.0×1=32 atm.
Equilibrium constant
Kp=pN2O4pNO22=1/3(2/3)2=1/34/9=34≈1.333.
Standard free energy change …
- KEAM 2026Set eng-2026-04174 marksMCQQ.The equilibrium constant KP of a homogenous equilibrium reaction is 1×10−6 at 227∘ C. What is the value of ΔG0 of the reaction at the same temperature? (R = 8.3JK−1mol−1) (A) 26.3 kJ mol-1 (B) +57.3 kJ mol-1 (C) -57.3 kJ mol-1 (D) -26.3 kJ mol-1 (E) -573 kJ mol-1
›Reveal solutionSolution
Since KP<1, lnKP is negative and ΔG0 is positive: about +57.3 kJ/mol.
T=227∘C=500 K, KP=1×10−6 so logKP=−6.
ΔG0=−2.303RTlogKP=−2.303×8.3×500×(−6). …
- KEAM 2026Set pha-2026-0419F4 marksMCQQ.Consider the equilibrium reaction, X(g)+Y(g)⇌W(g)+Z(g). The equilibrium constant KC for the reaction is 2.0×102 at 300 K and it decreases with increase in temperature. Which of the following is true for the reaction? (A) ΔH<0 (B) ΔG<0 (C) ΔS<0 (D) ΔH>0 (E) ΔS>0
›Reveal solutionSolution
By Le Chatelier / van't Hoff, if KC falls as T rises, raising temperature shifts equilibrium backward, so the forward reaction is exothermic: ΔH<0. …
- KEAM 2026Set pha-2026-0420F4 marksMCQQ.For the equilibrium A⇌B what is the value of log10K at 298 K? (ΔrH∘=−54.07 kJ mol−1, ΔrS∘=10 JK−1 and 2.303RT=5705) (A) 10 (B) 5 (C) 90 (D) 95 (E) 100
›Reveal solutionSolution
ΔG∘=−57050 J; log10K=57050/5705=10.
First compute the standard Gibbs energy:
ΔrG∘=ΔrH∘−TΔrS∘=−54070−(298)(10)=−54070−2980=−57050J mol−1. …
- KEAM 2025Set eng-2025-04234 marksMCQQ.In the reaction 3/2 O2(g)→O3(g), the value of ΔrG⊖ at 298 K is approximately (Kp=10−30 and 2.303RT=5.7 kJmol−1) (A) 171 kJ mol−1 (B) 191 kJ mol−1 (C) −171 kJ mol−1 (D) −191 kJ mol−1 (E) 100 kJ mol−1
›Reveal solutionSolution
The standard reaction Gibbs energy is about +171 kJ/mol.
Concept and Intuition
Standard reaction Gibbs energy relates to the equilibrium constant by Delta_r G = -2.303RT*log(Kp). A very small Kp (10^-30) means the reaction is highly non-spontaneous, giving a large positive Gibbs energy.
Step-by-Step Solution
- Delta_r G = -2.303RT*log(Kp).
- 2.303RT = 5.7 kJ/mol; log(Kp) = log(10^-30) = -30. …
- KEAM 2025Set eng-2025-04254 marksMCQQ.What is the log K of the following reaction, 2NH3(g)+CO2(g)⇌NH2CONH2(aq)+H2O(l) at 298 K If ΔrG∘=−11.4 kJ mol−1 and 2.303RT=5.7 kJ mol−1 (A) 2.5 (B) 1.5 (C) 4 (D) 3 (E) 2
›Reveal solutionSolution
Use ΔrG∘=−2.303RTlogK, so logK=−ΔrG∘/(2.303RT)=11.4/5.7=2.
The relation between standard free energy and equilibrium constant:
ΔrG∘=−2.303RTlogK ⇒ logK=2.303RT−ΔrG∘. …
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