Hydration Enthalpy (ΔHₕyd) JEE/NEET Concepts

Definition:

Hydration enthalpy is the energy released when 1 mole of gaseous ions gets surrounded by water molecules.

Always negative (exothermic)


Example:

Na⁺(g) → Na⁺(aq) + energy released


Factors Affecting Hydration Enthalpy

1. Size of Ion

Smaller ion → higher hydration enthalpy

✔️ Reason:

  • Higher charge density
  • Strong attraction with water

Order:
Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺


2. Charge on Ion

Higher charge → higher hydration enthalpy

✔️ Example:
Mg²⁺ > Na⁺


Group Trends

Group 1 elements

Decreases down the group
Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺


Group 2 elements

Decreases down the group
Be²⁺ > Mg²⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺


Comparison (Very Important)

Group 2 > Group 1 (hydration enthalpy)

✔️ Example:
Mg²⁺ > Na⁺

👉 Reason:

  • Higher charge (+2)
  • Stronger attraction with water

Applications

✔️ 1. Solubility

Higher hydration enthalpy → more soluble


✔️ 2. Stability of Ions in Solution

Small, highly charged ions are more stable in water


Fagan’s Rule (Polarisation Concept)

Definition:

Fajans’ Rule predicts whether a bond will be more ionic or covalent based on polarisation of ions.

More polarisation ⇒ more covalent character


What is Polarisation?

  • Cation distorts the electron cloud of the anion
  • This distortion = polarisation

Factors Affecting Polarisation

1. Size of Cation

  • Smaller cation → more polarising power → more covalent

✔️ Example:

  • Li⁺ > Na⁺ > K⁺ (in polarising power)

2. Charge on Cation

  • Higher charge → more polarisation

✔️ Example:

  • Al³⁺ > Mg²⁺ > Na⁺

3. Size of Anion

  • Larger anion → more easily polarised → more covalent

✔️ Example:

  • I⁻ > Br⁻ > Cl⁻ > F⁻

4. Charge on Anion

  • Higher negative charge → more polarisation

✔️ Example:

  • N³⁻ > O²⁻ > F⁻

5. Electronic Configuration (Important Exception Concept)

  • Cations with pseudo noble gas configuration (d¹⁰) show more polarisation than noble gas config

✔️ Example:

  • Cu⁺ (d¹⁰) > Na⁺ (noble gas)

✔️ 1. Compare Covalent Character:

  • LiCl > NaCl > KCl (LiCl most covalent)

✔️ 2. Melting Point Trend:

  • More covalent → lower melting point

✔️ Example:

  • AlCl₃ (covalent, low MP)
  • NaCl (ionic, high MP)

✔️ 3. Solubility:

  • Ionic → soluble in water
  • Covalent → soluble in organic solvents

Metallic & non-metallic trends in the periodic table

Metallic Character (Electropositive Nature)

Trend:

  • Down a group: ↑ increases
  • Across a period (L → R): ↓ decreases

Reason:

  • Down the group → atomic size ↑ → valence electrons easily lost
  • Across period → effective nuclear charge ↑ → electrons tightly held

✔️ Order Example:

  • Group 1: Li < Na < K < Rb < Cs
  • Period 3: Na > Mg > Al > Si > P > S > Cl

Exceptions in Metallic Character

1. Be vs Al

  • Normally metallic character ↓ across period
  • But: Al > Be (unexpected)

Reason:

  • Be has very high ionization energy
  • Al can lose electron easily (3p¹ electron is less tightly held)

2. Ga vs Al

  • Expected: Ga > Al (down group)
  • Actual: Al > Ga

Reason:

  • Poor shielding by d-electrons in Ga → higher effective nuclear charge → harder to lose electron

Non-Metallic Character (Electronegativity / Electron Gain)

Trend:

  • Down a group: ↓ decreases
  • Across a period (L → R): ↑ increases

Reason:

  • Across period → size ↓, attraction for electrons ↑
  • Down group → size ↑, attraction ↓

✔️ Order Example:

  • Group 17: F > Cl > Br > I
  • Period 2: Li < Be < B < C < N < O < F

JEE/NEET-ready summary of acidic, basic, neutral, and amphoteric oxides with examples + trends:


1. Acidic Oxides

Definition: Oxides that react with water to form acids or react with bases to give salt + water.

Examples:

  • CO₂, SO₂, SO₃, P₂O₅, N₂O₅, Cl₂O₇
  • Non-metal oxides

Reactions:

  • CO₂ + H₂O → H₂CO₃
  • SO₃ + 2NaOH → Na₂SO₄ + H₂O

Trend:

  • Non-metallic character ↑ ⇒ acidity ↑
  • Across a period: acidity increases
  • Down a group: acidity decreases

2. Basic Oxides

Definition: Oxides that react with water to form bases or react with acids to give salt + water.

Examples:

  • Na₂O, CaO, MgO, K₂O
  • Mostly metal oxides

Reactions:

  • Na₂O + H₂O → 2NaOH
  • CaO + 2HCl → CaCl₂ + H₂O

Trend:

  • Metallic character ↑ ⇒ basicity ↑
  • Down a group: basicity increases
  • Across a period: basicity decreases

3. Amphoteric Oxides

Definition: Oxides that react with both acids and bases.

Examples (VERY IMPORTANT for exams):

  • Al₂O₃, ZnO, BeO, SnO, PbO, Cr₂O₃

Reactions:

  • ZnO + 2HCl → ZnCl₂ + H₂O (acts basic)
  • ZnO + 2NaOH → Na₂ZnO₂ + H₂O (acts acidic)

Trend:

  • Found near metal–nonmetal boundary
  • Small size + high charge density → amphoteric behavior

4. Neutral Oxides

Definition: Oxides that do not react with acids or bases.

Examples:

  • CO, NO, N₂O

Trend:

  • Mostly simple molecules
  • No acidic or basic nature

IMPORTANT PERIODIC TREND (MOST ASKED)

Across a period (Left → Right):

Basic → Amphoteric → Acidic

Example (Period 3):
Na₂O → MgO → Al₂O₃ → SiO₂ → P₂O₅ → SO₃ → Cl₂O₇

Key shift:

  • Metals → Non-metals
  • Basic → Acidic

QUICK REVISION TABLE

TypeNatureExamples
BasicMetal oxidesNa₂O, CaO
AmphotericBothAl₂O₃, ZnO
AcidicNon-metal oxidesSO₃, CO₂
NeutralNo reactionCO, NO

EXAM TIPS

  • Al₂O₃, ZnO → always remember (amphoteric)
  • CO ≠ acidic (neutral!)
  • Higher oxidation state ⇒ more acidic oxide
    • Example: SO₂ < SO₃ (acidity increases)

MCQs

Q1. Arrange in increasing acidic nature:

A. CO₂ < SiO₂ < SO₃
B. SiO₂ < CO₂ < SO₃
C. SO₃ < CO₂ < SiO₂
D. CO₂ < SO₃ < SiO₂


Q2. Arrange in decreasing basic strength:

A. Na₂O > MgO > Al₂O₃
B. Al₂O₃ > MgO > Na₂O
C. MgO > Na₂O > Al₂O₃
D. Na₂O > Al₂O₃ > MgO


Q3. Arrange in increasing amphoteric character:

A. Na₂O < MgO < Al₂O₃
B. Al₂O₃ < MgO < Na₂O
C. MgO < Na₂O < Al₂O₃
D. Na₂O < Al₂O₃ < MgO


Q4. Arrange in increasing acidic strength:

A. SO₂ < SO₃ < Cl₂O₇
B. Cl₂O₇ < SO₃ < SO₂
C. SO₃ < SO₂ < Cl₂O₇
D. SO₂ < Cl₂O₇ < SO₃


Q5. Arrange in increasing basic character:

A. CaO < MgO < Na₂O
B. Na₂O < MgO < CaO
C. MgO < CaO < Na₂O
D. CaO < Na₂O < MgO


Q6. Arrange in increasing acidic nature:

A. P₂O₅ < SO₃ < Cl₂O₇
B. Cl₂O₇ < SO₃ < P₂O₅
C. SO₃ < P₂O₅ < Cl₂O₇
D. P₂O₅ < Cl₂O₇ < SO₃


Q7. Arrange in increasing basic strength:

A. BeO < MgO < CaO
B. CaO < MgO < BeO
C. MgO < BeO < CaO
D. BeO < CaO < MgO


Q8. Arrange in increasing acidic character:

A. N₂O₃ < NO₂ < N₂O₅
B. N₂O₅ < NO₂ < N₂O₃
C. NO₂ < N₂O₃ < N₂O₅
D. N₂O₃ < N₂O₅ < NO₂


ANSWERS

  1. B → SiO₂ < CO₂ < SO₃
  2. A → Na₂O > MgO > Al₂O₃
  3. A → Na₂O < MgO < Al₂O₃
  4. A → SO₂ < SO₃ < Cl₂O₇
  5. C → MgO < CaO < Na₂O
  6. A → P₂O₅ < SO₃ < Cl₂O₇
  7. A → BeO < MgO < CaO
  8. A → N₂O₃ < NO₂ < N₂O₅

SHORT TRICKS (VERY IMPORTANT)

  • Across period: Basic ↓, Acidic ↑
  • Down group: Basic ↑
  • Higher oxidation state ⇒ more acidic
  • Metal oxides → basic
  • Non-metal oxides → acidic
  • Border elements (Be, Al, Zn) → amphoteric

Electronegativity — JEE/NEET Complete Concepts

🔹 Definition

Electronegativity is the tendency of an atom to attract the shared pair of electrons towards itself in a chemical bond.


Important Points

  • Applies only to bonded atoms
  • It is a relative (dimensionless) value
  • Most commonly used scale → Pauling scale

Trends in Periodic Table

Across a Period (→)

Increases

  • Reason: Increase in nuclear charge → stronger pull on electrons

Down a Group (↓)

Decreases

  • Reason: Increase in size → weaker attraction

🔹 Important Order

Fluorine (F) is the most electronegative elementF > O > N > Cl > Br > I\textbf{F > O > N > Cl > Br > I}


Factors Affecting Electronegativity

  1. Atomic Size
    • Smaller atom → higher electronegativity
  2. Nuclear Charge
    • More protons → stronger attraction
  3. Shielding Effect
    • More shielding → lower electronegativity
  4. Hybridisation
    • sp > sp² > sp³

More s-character → electrons closer to nucleus


Important Exceptions


❗ Noble Gases

  • Usually no electronegativity
  • (Because they rarely form bonds)

Pauling Scale (Electronegativity) — JEE/NEET Concept

The Pauling scale is the most commonly used scale to measure electronegativity, proposed by Linus Pauling.


Basic Idea

Electronegativity is calculated based on:

✔ Bond energies (bond dissociation enthalpies)

  • If a bond A–B is stronger than expected, it means:
    A and B have different electronegativities

Formula (Conceptual)

Pauling related electronegativity difference to bond energy:χA−χB∝DAB−DAA+DBB2\chi_A – \chi_B \propto \sqrt{D_{AB} – \frac{D_{AA} + D_{BB}}{2}}

Where:

  • DABD_{AB} = bond energy of A–B
  • DAA,DBBD_{AA}, D_{BB}​ = bond energies of A–A and B–B

Key Points

  1. Fluorine is highest
    • Value = 4.0 (maximum on scale)
  2. Values are relative
    • Not absolute, just comparison
  3. Dimensionless
    • No unit

🔹 Example Values

ElementElectronegativity
F4.0
O3.5
N3.0
Cl3.0
H2.1

Important Applications

1. Predict Bond Type

  • ΔEN ≈ 0 → Non-polar covalent
  • ΔEN small → Polar covalent
  • ΔEN large → Ionic

2. Predict Polarity

  • Larger difference → more polar bond

Mulliken Scale — Electronegativity (JEE/NEET)

The Mulliken scale was proposed by Robert S. Mulliken.


Basic Idea

Electronegativity depends on:

✔ Ionisation Enthalpy (IE)
✔ Electron Gain Enthalpy (EGE / Electron Affinity)

So, it considers both:

  • Tendency to lose electron (IE)
  • Tendency to gain electron (EGE)

🔹 Formula

χ=IE+EGE2\chi = \frac{\text{IE} + \text{EGE}}{2}(In some books, electron affinity is used instead of EGE)


🔹 Meaning

  • Higher IE → atom doesn’t lose electrons easily
  • More negative EGE → atom gains electrons easily

✔ So, higher value = higher electronegativity


🔹 Key Points

  1. Absolute scale
    • Based on measurable energies (unlike Pauling)
  2. Applies to isolated atoms
    • Not bond-based
  3. Units initially in energy
    • Often converted to dimensionless values

🔹 Comparison with Pauling Scale

FeatureMullikenPauling
Based onIE + EGEBond energy
TypeAbsoluteRelative
ConceptAtomic propertyBond property

Basic Relation

The two scales are related approximately by:χPauling≈χMulliken2.8\chi_{\text{Pauling}} \approx \frac{\chi_{\text{Mulliken}}}{2.8}

Electron Gain Enthalpy (EGE) — JEE/NEET Complete Concepts

🔹 Definition

Electron Gain Enthalpy is the enthalpy change when an electron is added to an isolated gaseous atom.

  • Usually negative (energy released)
  • More negative = greater tendency to gain electron

🔹 Representation

X(g)+e−→X−(g)X(g) + e^- \rightarrow X^-(g)


🔹 General Trends

Across a Period (Left → Right)

EGE becomes more negative

Reason:

  • Increase in nuclear charge → stronger attraction for incoming electron

Down a Group (Top → Bottom)

EGE becomes less negative

Reason:

  • Increase in size → electron added far from nucleus → less attraction

IMPORTANT EXCEPTIONS (Very Important for JEE/NEET)


❗ Exception 1: Be, Mg (Group 2)

EGE ≈ zero or slightly positive

Reason:

  • Stable ns² configuration
  • Incoming electron enters higher energy p-orbital

❗ Exception 2: N (Group 15)

EGE is less negative than expected

Reason:

  • Stable half-filled configuration (np³)
  • Adding electron causes electron-electron repulsion

❗ Exception 3: Noble Gases (Group 18)

EGE is positive

Reason:

  • Completely filled orbitals → very stable
  • Electron must enter new shell → requires energy

❗ Exception 4: Fluorine vs Chlorine

👉 Cl has more negative EGE than F ❗

❌ Expected: F > Cl
✅ Actual: Cl > F

Reason:

  • F is very small → strong electron-electron repulsion in 2p orbital
  • Cl has larger size → less repulsion → easier electron addition

🔹 Important Order Example

Among halogens:
Cl > F > Br > I


Successive Electron Gain Enthalpy

👉 Adding 2nd electron:X−+e−→X2−X^- + e^- \rightarrow X^{2-}

❗ Always positive
Reason:

  • Electron added to already negative ion → strong repulsion

🔹 Elements in Group 16

  • Oxygen (O)
  • Sulfur (S)
  • Selenium (Se)
  • Tellurium (Te)
  • Polonium (Po)

Increases down the group
O < S < Se < Te


Why is the 2nd Electron Gain Enthalpy of Oxygen Positive?

Consider the process:O−(g)+e−→O2−(g)\text{O}^- (g) + e^- \rightarrow \text{O}^{2-} (g)


🔹 Key Reason: Electron–Electron Repulsion

After gaining one electron:

  • Oxygen becomes O⁻ (negatively charged)

Now, adding another electron:

  • Incoming electron is repelled by the already negative ion

✔ So, energy must be supplied → EGE becomes positive

Isoelectronic Species (JEE/NEET Concept)

Isoelectronic species are:

Atoms, ions, or molecules that have the same number of electrons.


🔹 Examples

  • N³⁻, O²⁻, F⁻, Ne, Na⁺, Mg²⁺

All of these have 10 electrons → so they are isoelectronic


How to identify?

Just count total electrons

Example:

  • O²⁻ → 8 + 2 = 10 electrons
  • F⁻ → 9 + 1 = 10 electrons
  • Na⁺ → 11 − 1 = 10 electrons

✔ Same electrons → Isoelectronic


🔹 Important Trend (VERY IMPORTANT for JEE/NEET)

In an isoelectronic series:

Size decreases as nuclear charge (Z) increases


Example Order of Size

For species with 10 electrons:

N³⁻ > O²⁻ > F⁻ > Ne > Na⁺ > Mg²⁺

Reason:

  • All have same electrons
  • But increasing protons (Z) pull electrons closer → size decreases

🔹 Key Exam Line

“Isoelectronic species have same number of electrons but different nuclear charge.”