This MCQ module is based on: D Block Compounds
D Block Compounds
This assessment will be based on: D Block Compounds
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D Block Compounds
Two Star Chemicals of the d-Block
Two compounds dominate Class 12 d-block chemistry — the orange-red potassium dichromate K₂Cr₂O₇ (Cr in the +6 state) and the deep-purple potassium permanganate KMnO₄ (Mn in the +7 state). Both are powerful oxidising agents, both are used as primary standards in volumetric analysis, and both arise from chromium and manganese ores by very similar industrial routes.
8.14 Oxides and Oxoanions of the 3d Series
Transition metals burn in oxygen at high temperature to form oxides. The maximum oxidation state of the metal in its oxide equals its group number up to Mn:
| Group | 3 | 4 | 5 | 6 | 7 |
|---|---|---|---|---|---|
| Highest oxide | Sc₂O₃ | TiO₂ | V₂O₅ | CrO₃ | Mn₂O₇ |
| Oxidation state | +3 | +4 | +5 | +6 | +7 |
Beyond Mn the maximum drops sharply (Fe₂O₃ is the highest iron oxide). As the metal's oxidation number rises, ionic character drops and acidic character rises: Mn₂O₇ is a covalent green oil that gives HMnO₄ in water; CrO₃ gives H₂CrO₄ and H₂Cr₂O₇.
8.15 Potassium Dichromate, K₂Cr₂O₇
8.15.1 Preparation from Chromite Ore
The starting material is the mineral chromite ore FeCr₂O₄. Three steps convert it to K₂Cr₂O₇.
Step 1 — Oxidative fusion with alkali in air (~1300 K). Sodium chromate is produced.
Step 2 — Acidify the chromate to form sodium dichromate. The yellow chromate (CrO₄²⁻) solution is filtered (Fe₂O₃ removed) and treated with H₂SO₄.
Orange Na₂Cr₂O₇·2H₂O crystallises out.
Step 3 — Convert to less soluble potassium dichromate by metathesis with KCl.
K₂Cr₂O₇ is much less soluble than Na₂Cr₂O₇, so orange-red crystals separate on cooling.
8.15.2 Chromate ⇌ Dichromate Equilibrium
Chromate (CrO₄²⁻) and dichromate (Cr₂O₇²⁻) are interconvertible. Adding acid shifts the equilibrium to dichromate (orange); adding base shifts it back to chromate (yellow). The Cr oxidation number is +6 in both.
8.15.3 Structure of CrO₄²⁻ and Cr₂O₇²⁻
CrO₄²⁻ is a regular tetrahedron: a central Cr surrounded by four O atoms at the corners. Cr₂O₇²⁻ is two such tetrahedra joined at one corner (a shared O atom). The Cr–O–Cr bridge angle is 126°.
8.15.4 Properties & Oxidising Action in Acidic Medium
K₂Cr₂O₇ forms bright orange-red crystals, m.p. 671 K. It is moderately soluble in water and is a stable, weighable solid — making it a perfect primary standard in volumetric analysis. In dilute H₂SO₄ it acts as a powerful oxidiser:
Three Standard Oxidation Reactions (acidic medium)
(a) Iodide → Iodine:
(b) Iron(II) → Iron(III):
(c) Hydrogen sulphide → Sulphur:
Other reductants similarly oxidised: Sn²⁺ → Sn⁴⁺; SO₃²⁻ → SO₄²⁻; alcohols → aldehydes/ketones (used to spot drunk drivers in a "breathalyser" — the orange Cr(VI) turns green Cr(III) in presence of ethanol).
8.15.5 Uses of K₂Cr₂O₇
- Tanning of leather (chrome tanning).
- Primary standard in volumetric analysis (e.g., for Fe²⁺ titrations).
- Manufacture of azo dyes.
- Cleaning glassware (chromic-acid mixture).
- Oxidant in synthetic organic chemistry.
Q. Balance the reaction of acidified K₂Cr₂O₇ with FeSO₄ in ionic form and identify the colour change observed.
Cr₂O₇²⁻ (orange) gains 6 electrons per ion; each Fe²⁺ → Fe³⁺ loses 1 electron — so 6 Fe²⁺ are needed.
Colour change: orange (Cr⁶⁺) → green (Cr³⁺); pale green Fe²⁺ → pale yellow Fe³⁺.
8.16 Potassium Permanganate, KMnO₄
8.16.1 Laboratory and Industrial Preparation
The starting material is pyrolusite ore (MnO₂). Two steps convert MnO₂ to KMnO₄.
Step 1 — Alkaline oxidative fusion with KOH and air (or KNO₃) gives the dark green manganate ion (Mn⁶⁺):
Step 2 — Convert manganate to permanganate. Two routes are used.
Route A — disproportionation (lab method): in neutral or acidic medium,
Route B — electrolytic oxidation (industrial method): in alkaline solution, the manganate is oxidised at the anode to permanganate:
Laboratory route from a Mn(II) salt: peroxodisulphate oxidises Mn²⁺ all the way to MnO₄⁻ (Ag⁺ catalysed):
8.16.2 Properties
KMnO₄ forms dark purple (almost black) rhombic crystals, isostructural with KClO₄. It is moderately soluble in water (6.4 g per 100 g at 293 K) giving an intensely purple solution. On heating to 513 K it decomposes:
The MnO₄⁻ ion is tetrahedral with strong π-bonding (oxygen 2p with manganese 3d). The intense colour is due to a charge-transfer transition (oxygen → metal); MnO₄⁻ has no unpaired d-electrons, so it is diamagnetic (the slight temperature-dependent paramagnetism comes from molecular-orbital effects beyond NCERT scope). MnO₄²⁻ (manganate, Mn⁶⁺ d¹) is paramagnetic with one unpaired electron.
8.16.3 Structure of MnO₄⁻ Ion
8.16.4 Oxidising Power Depends on pH
Three half-reactions are crucial — and the medium decides the product.
| Medium | Half-reaction | Product | E° / V |
|---|---|---|---|
| Acidic (H⁺) | MnO₄⁻ + 8 H⁺ + 5 e⁻ → Mn²⁺ + 4 H₂O | Mn²⁺ (pale pink) | +1.52 |
| Neutral / faint alkaline | MnO₄⁻ + 4 H⁺ + 3 e⁻ → MnO₂ + 2 H₂O | MnO₂ (brown solid) | +1.69 |
| Strongly alkaline | MnO₄⁻ + e⁻ → MnO₄²⁻ | MnO₄²⁻ (green) | +0.56 |
Standard Reactions in Acidic Medium
(a) Iodide → Iodine:
(b) Fe(II) (green) → Fe(III) (yellow):
(c) Oxalate / oxalic acid → CO₂ (at 333 K):
(d) Hydrogen sulphide → Sulphur:
(e) SO₃²⁻ / SO₂ → SO₄²⁻:
(f) Nitrite → Nitrate:
Reactions in Neutral / Faintly Alkaline Medium
(a) Iodide → Iodate:
(b) Thiosulphate → Sulphate:
(c) Mn²⁺ → MnO₂ (catalysed by ZnSO₄ or ZnO):
8.16.5 Uses of KMnO₄
- Strong oxidant in synthetic organic chemistry (Baeyer's reagent — alkaline KMnO₄ — tests unsaturation).
- Volumetric analysis (self-indicating in acid; pink end-point).
- Decolourising oils and bleaching wool, cotton, silk.
- Mild antiseptic (dilute solutions for skin disinfection).
- Water purification (oxidises Fe²⁺ and H₂S).
Interactive: KMnO₄ Reaction Predictor by Medium L3 Apply
Choose a reductant and the reaction medium — the simulator returns the balanced ionic equation, the Mn product (Mn²⁺ vs MnO₂ vs MnO₄²⁻) and the visible colour change.
Aim: Track the oxidation state of manganese at each step of the KMnO₄ industrial preparation.
Procedure:
- Write the molecular formula of pyrolusite. Determine the oxidation state of Mn.
- Write the formula of the green intermediate K₂MnO₄. Determine the oxidation state of Mn.
- Write the formula of KMnO₄. Determine the oxidation state of Mn.
- Plot the oxidation states across the three stages and identify which oxidant is responsible for each step.
Predict: How many electrons must Mn lose, in total, between MnO₂ and KMnO₄?
MnO₂: Mn = +4 · K₂MnO₄: Mn = +6 · KMnO₄: Mn = +7.
Step 1 (MnO₂ → MnO₄²⁻): Mn loses 2 e⁻; oxidant = O₂ (or KNO₃).
Step 2 (MnO₄²⁻ → MnO₄⁻): Mn loses 1 e⁻; oxidant = electrolytic anode (industrial) or H⁺ via disproportionation (lab).
Total e⁻ lost = 3 per Mn atom from pyrolusite to permanganate.
Q. Write the balanced ionic equation for the reaction between acidified KMnO₄ and ferrous oxalate, FeC₂O₄, in solution. (FeC₂O₄ contains both Fe²⁺ and C₂O₄²⁻ as reductants.)
Fe²⁺ → Fe³⁺ loses 1 e⁻; C₂O₄²⁻ → 2 CO₂ loses 2 e⁻; so each FeC₂O₄ unit loses 3 e⁻. Each MnO₄⁻ accepts 5 e⁻.
LCM = 15: take 3 MnO₄⁻ and 5 FeC₂O₄.
Q (In-text 4.6). Why is the highest oxidation state of a metal exhibited only in its oxide or fluoride?
Both O and F have small atomic size and very high electronegativity. They strip every accessible valence electron off the metal and stabilise the resulting high-charge cation through (i) very high lattice/bond energy and (ii) pπ-dπ multiple bonding (in the case of O, e.g. Mn=O bonds in Mn₂O₇). No other element offers both effects together.
Competency-Based Questions L3 L4
Q1. (MCQ) The bridge angle Cr–O–Cr in the dichromate ion is approximately:
Q2. (MCQ) When acidified KMnO₄ reacts with oxalic acid, the manganese is reduced from:
Q3. (SA) Why is K₂Cr₂O₇ preferred over Na₂Cr₂O₇ as a primary standard?
Q4. (LA) KMnO₄ titrations are always carried out in dilute H₂SO₄ — never in HCl. Explain.
Q5. (HOT) Both Cr₂O₇²⁻ and MnO₄⁻ contain the metal in its highest oxidation state, yet MnO₄⁻ is a stronger oxidant. Suggest two reasons.
Assertion–Reason Questions L4 L5
Choose: A) Both A and R true and R explains A · B) Both true but R does not explain A · C) A true, R false · D) A false, R true.
Assertion (A): The dichromate ion is orange while the chromate ion is yellow.
Reason (R): Adding acid to a yellow chromate solution converts it into orange dichromate.
Assertion (A): KMnO₄ is diamagnetic at room temperature.
Reason (R): The MnO₄⁻ ion contains Mn(VII) which has a d⁰ configuration — no unpaired electrons.
Assertion (A): KMnO₄ titrations are conducted in H₂SO₄ rather than HCl.
Reason (R): HCl reacts with KMnO₄ to release Cl₂, introducing error in the titration.
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