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Q.59 Chemistry ⭐ 360° Option Elimination Active
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NEET 2025 Chemistry Question 59 Solution

Topic: Equilibrium · Official NTA Booklet Code 45
NEET 2025 Chemistry Question 59: Ionization Constants and Stepwise Dissociation of Phosphoric Acid (H₃PO₄)

Question

Phosphoric acid ionizes in three steps with their ionization constant values Ka₁, Ka₂ and Ka₃, respectively, while K is the overall ionization constant. Which of the following statements are true? A. log K = log Ka₁ + log Ka₂ + log Ka₃ B. H₃PO₄ is a stronger acid than H₂PO₄⁻ and HPO₄²⁻. C. Ka₁ > Ka₂ > Ka₃ D. Ka₁ = (Ka₃ + Ka₂)/2 Choose the correct answer from the options given below:

✓
Verified Against NTA Final Answer Key
Option (4) : A, B and C only
📚 Equilibrium Easy
📋 Given Parameters & Problem Setup
Step 1 Ionization Constant K_{a1}
Step 2 Ionization Constant K_{a2}
Step 3 Ionization Constant K_{a3}
Overall Constant K = K_{a1} · K_{a2} · K_{a3}
Statements A: log K = log K_{a1} + log K_{a2} + log K_{a3}; B: H₃PO₄ stronger than H₂PO₄⁻ and HPO₄²⁻; C: K_{a1} > K_{a2} > K_{a3}; D: K_{a1} = (K_{a3} + K_{a2})/2
⚡

The 30-Second Exam Hall Shortcut: ⚡ Polyprotic Acid Ionization Triad

⏱️ Save ~35 seconds

Overall K is the product: K = K₁ K₂ K₃ ⟹ log K = Σ log K_i (A is TRUE)! Neutral acid loses H⁺ much easier than negative anions ⟹ H₃PO₄ is strongest (B is TRUE)! Stepwise constants drop by orders of magnitude: K_{a1} >> K_{a2} >> K_{a3} (C is TRUE)! Arithmetic mean D is absurd! ⟹ A, B, and C only!

1 Recall polyprotic acid equilibrium: For multi-step ionization, the overall equilibrium constant is the PRODUCT of stepwise constants: K = K_{a1} × K_{a2} × K_{a3}.
2 Taking log on both sides: log K = log K_{a1} + log K_{a2} + log K_{a3}. Statement A is TRUE.
3 Acid strength comparison: Removing a proton from neutral H₃PO₄ requires far less energy than from negatively charged H₂PO₄⁻ or doubly charged HPO₄²⁻. Thus H₃PO₄ is a stronger acid than its conjugate species. Statement B is TRUE.
4 Stepwise constants: K_{a1} (7.5 × 10⁻³) >> K_{a2} (6.2 × 10⁻⁸) >> K_{a3} (4.2 × 10⁻¹³). Statement C is TRUE.
5 Statement D proposes an arithmetic average between constants differing by 10⁵, which is mathematically false.
6 Conclusion: A, B and C only are true.
7 Match Option (4) in under 15 seconds!
🛡️
Why You Can 100% Trust This Shortcut: Successive Ionization of Polybasic Acids (NCERT Chemistry · Equilibrium: K_a1 >> K_a2 >> K_a3).
📐

Step-by-Step Rigorous Workflow & Mathematical Proof

Step 1

Stepwise Dissociation of Phosphoric Acid and Product Rule

Phosphoric acid (H₃PO₄) is a tribasic mineral acid ionizing in three consecutive stages:

Overall: H3PO4⇌3H++PO43−,K=Ka1×Ka2×Ka3\text{Overall: } \text{H}_3\text{PO}_4 \rightleftharpoons 3\text{H}^+ + \text{PO}_4^{3-}, \quad K = K_{a1} \times K_{a2} \times K_{a3}
  • • Taking logarithms of both sides converts the multiplication into addition:
  • • \log K = \log K_{a1} + \log K_{a2} + \log K_{a3}.
  • • Thus Statement A is rigorously TRUE.
Step 2

Analyze Relative Acid Strengths (Statement B and C)

Electrostatic principles dictate the relative difficulty of successive proton removals:

Ka1(7.5×10−3)≫Ka2(6.2×10−8)≫Ka3(4.2×10−13)K_{a1} (7.5 \times 10^{-3}) \gg K_{a2} (6.2 \times 10^{-8}) \gg K_{a3} (4.2 \times 10^{-13})
  • • It is far easier to remove a positively charged proton from a neutral molecule (H₃PO₄) than from a negatively charged ion (H₂PO₄⁻), and even harder from a doubly negative ion (HPO₄²⁻).
  • • Consequently, H₃PO₄ is a significantly stronger acid than H₂PO₄⁻ and HPO₄²⁻ (Statement B is TRUE).
  • • The hierarchy K_{a1} > K_{a2} > K_{a3} holds universally for all polybasic acids (Statement C is TRUE).
Step 3

Evaluate Statement D and Select Option

Statement D asserts that K_{a1} = (K_{a3} + K_{a2}) / 2. Because these equilibrium constants differ by orders of magnitude (10⁻³ vs 10⁻⁸ vs 10⁻¹³), an arithmetic mean is physically and mathematically impossible. Statement D is FALSE.

Statements A, B, and C are TRUE; Statement D is FALSE  ⟹  Option (4)\text{Statements A, B, and C are TRUE; Statement D is FALSE} \implies \text{Option (4)}
  • • Matches Option (4) exactly.
⭐

360° Option Elimination Engine Key Feature

Diagnose every choice: Know exactly why the right option works and why distractors fail.

4-Option Deep Scan
1 A
✗ Incorrect
Verdict & Scientific Reason:

Incorrect. Statement C (K_{a1} > K_{a2} > K_{a3}) is also true.

⚠️
Student Fallacy (Why candidates pick this trap): Omitting statement C.
2 B
✗ Incorrect
Verdict & Scientific Reason:

Incorrect. Statement B is also true.

⚠️
Student Fallacy (Why candidates pick this trap): Doubting whether neutral acid is stronger than its conjugate bases.
3 C
✗ Incorrect
Verdict & Scientific Reason:

Incorrect. Statement D is false and A is omitted.

⚠️
Student Fallacy (Why candidates pick this trap): Believing in an arithmetic average relation between Ka values.
4 D
✓ 100% Correct
Verdict & Scientific Reason:

100% correct. Statements A (log product), B (acid strength), and C (stepwise hierarchy) are true.

💡
Why this is airtight: None; complete mastery of polyprotic acids.
⚠️

NTA Trap Alert: Second-Guessing Relative Acid Strength (Statement B)

Some students hesitate on Statement B, wondering if an amphiprotic anion could somehow act as a stronger acid. Electrostatic attraction ensures neutral parent acid is ALWAYS much stronger than its negative conjugate anions!

🛡️ How to avoid the -1 mark: Law of polyprotic acids: Neutral acid is always strongest: K_{a1} >> K_{a2} >> K_{a3}!
📖

Core NEET Syllabus Standard

NEET Chemistry Core Syllabus · Equilibrium Standard Benchmark
Core Scientific Principle Tested:

"K = K₁·K₂·K₃ ⟹ log K = Σ log K_i; K_{a1} > K_{a2} > K_{a3}."

Syllabus Focus: Ionization of Polybasic Acids and Overall Equilibrium Constant
✓ Core NEET UG Syllabus Anchor Syllabus & Academic Standards ↗
K multiplies (A), neutral is strongest (B), K drops stepwise (C) ⟹ A, B, C are TRUE!

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