Acidity & Basicity in Hydrocarbons: From Alkynes to Arenes
Master the acidity trends in hydrocarbons and basicity differences in nitrogen heterocycles with mechanisms and JEE applications.
Why Acidity & Basicity Trends Matter in JEE
Understanding acidity and basicity in hydrocarbons is crucial for solving complex organic chemistry problems in JEE. These concepts appear in:
- Reaction mechanism prediction and arrow-pushing
- Compound stability and reactivity comparisons
- Acid-base equilibrium problems
- Synthesis planning and reagent selection
Acidity of Terminal Alkynes vs Alkanes/Alkenes
📊 Acidity Trend:
🔬 Why Terminal Alkynes are Acidic:
1. Hybridization Effect:
• Terminal alkyne H is attached to sp-hybridized carbon (50% s-character)
• Alkane H is attached to sp³-hybridized carbon (25% s-character)
• Higher s-character → electrons closer to nucleus → more acidic H
2. Stability of Conjugate Base:
• Acetylide ion is stabilized by sp-hybridization and triple bond
• Carbanions from alkanes are highly unstable
🎯 JEE Application Example:
Problem: Which hydrogen is most acidic and why?
Solution: HC≡CH (terminal alkyne) is most acidic because:
• sp-hybridization (50% s-character)
• Conjugate base HC≡C:⁻ is stabilized by triple bond
• pKₐ ≈ 25 compared to ≈44-50 for others
Basicity: Pyridine vs Pyrrole
📊 Basicity Trend:
⚖️ Comparative Analysis:
Pyridine (More Basic):
- Nitrogen is sp² hybridized
- Lone pair in sp² orbital
- Lone pair not involved in aromaticity
- Available for protonation
- pKₐ ≈ 5.2
Pyrrole (Less Basic):
- Nitrogen is sp² hybridized
- Lone pair in p orbital
- Lone pair involved in aromatic sextet
- Protonation destroys aromaticity
- pKₐ ≈ 0.4
🔬 Key Factor: Aromaticity Preservation
Pyridine Protonation:
• Lone pair not part of aromatic system
• Protonation doesn't affect aromaticity
• Conjugate acid remains aromatic
Pyrrole Protonation:
• Lone pair essential for aromatic sextet
• Protonation destroys aromaticity
• High energy penalty makes it less basic
🚀 Problem-Solving Strategies
For Acidity Comparisons:
- Check hybridization (sp > sp² > sp³)
- Look at conjugate base stability
- Consider resonance and induction effects
- Remember: pKₐ ↓ = acidity ↑
For Basicity Comparisons:
- Check if lone pair is available
- Consider aromaticity preservation
- Look at hybridization effects
- Remember: pKₐ ↑ = basicity ↑
💡 Memory Aid
Acidity Mnemonic
S - s-character
P - Proton removal
A - Anion stability
R - Resonance effects
K - Kₐ value
Basicity Rule
A - Available lone pair
L - Localized electrons
P - Preserve aromaticity
📝 Quick Self-Test
Try these JEE-level problems to test your understanding:
1. Arrange in decreasing acidity: CH₄, HC≡CH, NH₃, H₂O
2. Explain why pyrrole is less basic than pyridine but more acidic
3. Which is stronger base: aniline or ammonia? Justify
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