Q.An organic compound (A) with molecular formula C8H8O forms an orange-red precipitate with 2,4-DNP reagent and gives yellow precipitate on heating with iodine in the presence of sodium hydroxide. It neither reduces Tollens' or Fehlings' reagent, nor does it decolourise bromine water or Baeyer's reagent. On drastic oxidation with chromic acid, it gives a carboxylic acid (B) having molecular formula C7H6O2. Identify the compounds (A) and (B) and explain the reactions involved.
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Oxidation Reactions
Alcohol Oxidation: The Intuition First
Imagine you have a molecule of ethanol — the alcohol in your hand sanitizer or a drink. It has a carbon atom bonded to an –OH group. Now picture that –OH group as a "handle" that can be transformed. Oxidation, in organic chemistry, doesn't always mean adding oxygen — it often means removing hydrogen from a carbon that already has a bond to oxygen. For alcohols, oxidation is like "stripping away" hydrogen atoms from the carbon that holds the –OH, turning the alcohol into a more oxidized functional group.
Think of it this way: a primary alcohol (R–CH₂–OH) has two hydrogens on the carbon with the –OH. If you remove one hydrogen and the hydrogen from the –OH, you get an aldehyde (R–CHO). Remove both hydrogens (and the –OH hydrogen), and you get a carboxylic acid (R–COOH). A secondary alcohol (R–CHOH–R') has only one hydrogen on that carbon — remove it, and you get a ketone (R–CO–R'). A tertiary alcohol has no hydrogen on that carbon — so it cannot be oxidized without breaking the carbon skeleton.
That's the core intuition: oxidation of an alcohol is about removing hydrogens from the carbon bearing the –OH group. The more hydrogens you can remove, the more oxidized the product.
The Precise Statement
Alcohol oxidation is the process in which an alcohol loses hydrogen atoms (dehydrogenation) from the carbon bonded to the –OH group, increasing the number of C–O bonds (or decreasing C–H bonds). The outcome depends on the class of the alcohol:
| Alcohol Class | Structure | Product after oxidation | Reagent example |
|---|---|---|---|
| Primary (1°) | R–CH₂–OH | Aldehyde (R–CHO) then Carboxylic acid (R–COOH) | PCC (stops at aldehyde); K₂Cr₂O₇/H⁺ (goes to acid) |
| Secondary (2°) | R–CHOH–R' | Ketone (R–CO–R') | K₂Cr₂O₇/H⁺, CrO₃, etc. |
| Tertiary (3°) | R₃C–OH | No reaction (under normal conditions) | — |
A common mistake: students think "oxidation" always adds oxygen. For alcohols, it's removal of hydrogen from the carbon with the –OH. The oxygen from the –OH stays — it's the hydrogens that leave.
Why Does Tertiary Alcohol Not Oxidize?
Look at the carbon with the –OH in a tertiary alcohol: it has three carbon groups attached and no hydrogen. To form a C=O bond, you'd need to remove a hydrogen from that carbon — but there is none. The only way to oxidize a tertiary alcohol is to break a C–C bond (strong and difficult), which is not typical oxidation. So in standard organic chemistry, tertiary alcohols are inert to mild oxidizing agents.
A Real-World Analogy
Think of the alcohol carbon as a "parking spot" with a certain number of hydrogen "cars." Primary alcohol has two cars parked. Oxidation is like towing away one car (→ aldehyde) or both cars (→ carboxylic acid). Secondary alcohol has one car — tow it away, and you get a ketone. Tertiary alcohol has zero cars — nothing to tow, so no reaction.
Key Reagents to Remember (for exams)
- PCC (pyridinium chlorochromate): oxidizes 1° alcohols to aldehydes only — stops there.
- K₂Cr₂O₇ / H₂SO₄ (Jones reagent): oxidizes 1° alcohols all the way to carboxylic acids; 2° alcohols to ketones.
- KMnO₄: similar to dichromate, but stronger — can over-oxidize. …
Why this formula?
Oxidation Reactions: Why the Key Principles Hold
Oxidation reactions are fundamental to chemistry, and understanding why they work the way they do is essential for mastering Indian board exams (Class 11, 12, JEE, NEET). Let's break down the core ideas from first principles.
1. The Core Definition: What Does "Oxidation" Really Mean?
Historically, oxidation meant "adding oxygen." But that's too narrow. The modern, exam-correct definition is:
Oxidation is the loss of electrons by a species.
This is the electronic concept (given by the ionic theory). The why behind this definition comes from the behavior of atoms during chemical reactions.
Why do atoms lose electrons?
Atoms seek stability. They achieve this by having a full outer electron shell (octet, duplet, or pseudo-inert gas configuration).
- Metals (like Na, Mg, Fe) have few valence electrons (1, 2, or 3). It's energetically easier for them to lose these electrons than to gain 5, 6, or 7.
- Non-metals (like O, Cl, F) have many valence electrons (5, 6, or 7). It's energetically easier for them to gain electrons.
So, when a metal reacts with a non-metal, the metal loses electrons (gets oxidized), and the non-metal gains electrons (gets reduced).
Example:
2Na+Cl2→2NaCl
- Na loses 1 electron: Na→Na++e− (Oxidation)
- Cl gains 1 electron: Cl2+2e−→2Cl− (Reduction)
Key takeaway: Oxidation and reduction always happen together (Redox reactions). You cannot have one without the other.
2. The Key Formula(e): Oxidation Number Rules
The oxidation number (O.N.) is a bookkeeping tool. It's not a real charge (except in ionic compounds), but it helps track electron flow.
Why do we assign oxidation numbers?
Because in covalent compounds (like CH4 or H2O), electrons are shared, not transferred. We need a way to pretend they are transferred to see which atom "owns" the electrons more.
The Rules (and why they exist)
| Rule | Statement | Why this rule? |
|---|---|---|
| 1 | O.N. of an element in its free state = 0 | No electron transfer has occurred. |
| 2 | O.N. of a monatomic ion = its charge | The atom has actually lost/gained that many electrons. |
| 3 | O.N. of H = +1 (except in metal hydrides where it's -1) | H is less electronegative than O, F, Cl, but more electronegative than metals. |
| 4 | O.N. of O = -2 (except in peroxides where it's -1, superoxides -1/2, and with F where it's +2) | O is highly electronegative (3.44 on Pauling scale). It "pulls" electrons toward itself. |
| 5 | Sum of O.N. in a neutral compound = 0 | The compound has no net charge. |
| 6 | Sum of O.N. in a polyatomic ion = charge of the ion | The ion's overall charge must be accounted for. |
The Derivation of a Key Formula: Finding O.N. of an Unknown Element
Suppose you need to find the O.N. of S in H2SO4.
Step 1: Write known O.N.s:
- H: +1 (rule 3)
- O: -2 (rule 4)
- S: let it be x (unknown)
Step 2: Apply rule 5 (neutral compound sum = 0):
2(+1)+x+4(−2)=0
Step 3: Solve:
2+x−8=0
x−6=0
x=+6
Why this works: The oxidation number is a mathematical consequence of the electronegativity hierarchy. Oxygen is more electronegative than sulfur, so it "takes" the electrons. Hydrogen is less electronegative than sulfur, so it "gives" electrons to sulfur. The net result is that sulfur appears to have lost 6 electrons.
3. The Key Formula(e): Balancing Redox Equations
Two methods are exam-critical: Oxidation Number Method and Ion-Electron Method (Half-Reaction Method).
Why do we need these methods?
Because in a redox reaction, the total number of electrons lost (oxidation) must equal the total number of electrons gained (reduction). This is the Law of Conservation of Charge.
The Ion-Electron Method (for acidic medium) — Step-by-step why
Example: Balance MnO4−+Fe2+→Mn2++Fe3+ (acidic)
Step 1: Write half-reactions.
-
Oxidation: Fe2+→Fe3++e−
Why? Fe loses 1 electron (O.N. goes from +2 to +3).
-
Reduction: MnO4−→Mn2+
Why? Mn gains electrons (O.N. goes from +7 to +2).
Step 2: Balance atoms other than H and O.
- Mn is already balanced (1 on each side).
Step 3: Balance O by adding H2O.
- Left: 4 O atoms. Right: 0 O atoms.
- Add 4 H2O to the right:
MnO4−→Mn2++4H2O
Step 4: Balance H by adding H+ (because acidic medium).
- Right: 8 H atoms (from 4 H2O). Left: 0 H atoms.
- Add 8 H+ to the left:
8H++MnO4−→Mn2++4H2O
Step 5: Balance charge by adding electrons.
- Left: 8(+1)+(−1)=+7 charge.
- Right: +2 charge.
- To make left = right, add 5 electrons to the left:
8H++MnO4−+5e−→Mn2++4H2O
Step 6: Multiply half-reactions to equalize electrons.
- Oxidation: Fe2+→Fe3++e− (×5)
- Reduction: 8H++MnO4−+5e−→Mn2++4H2O (×1)
Step 7: Add them:
5Fe2++8H++MnO4−→5Fe3++Mn2++4H2O
Why this works: Every step is driven by conservation laws:
- Mass balance: Same number of each atom on both sides.
- Charge balance: Net charge on left = net charge on right.
- Electron balance: Electrons lost = electrons gained.
4. The Key Formula(e): Electrochemical Series and Cell Potential
For a galvanic cell (voltaic cell), the cell potential Ecell∘ is:
Ecell∘=Ecathode∘−Eanode∘
Why this formula? …
Concept: Oxidation Reactions — The compound is a methyl ketone that undergoes iodoform reaction and is oxidised to a benzoic acid derivative.
Step 1 — Functional group clues
The orange-red precipitate with 2,4-DNP confirms a carbonyl group (C=O). The positive iodoform test (yellow precipitate of CHIX3) indicates a methyl ketone (COCHX3) or a secondary alcohol oxidisable to one. Since it does not reduce Tollens’/Fehling’s reagent, it is not an aldehyde. It does not decolourise bromine water or Baeyer’s reagent, so there is no carbon-carbon double bond.
Step 2 — Molecular formula and oxidation product …
The clues point to an aromatic methyl ketone with no C=C double bond and no aldehyde group. Compound (A) is acetophenone (C6H5COCH3) and (B) is benzoic acid (C6H5COOH).
Reading the clues
- Molecular formula C8H8O -> degree of unsaturation =22(8)+2−8=5 (a benzene ring = 4, plus one C=O).
- Orange-red precipitate with 2,4-DNP -> a carbonyl group (>C=O) is present.
- Yellow precipitate with I2/NaOH (iodoform test) -> a CH3CO− (methyl ketone) group is present.
- Does not reduce Tollens or Fehling reagent -> it is not an aldehyde (so the carbonyl is a ketone).
- Does not decolourise bromine water or Baeyer reagent -> no C=C or C≡C; the only unsaturation besides the ring is the carbonyl.
- Drastic oxidation with chromic acid -> C7H6O2 (benzoic acid) -> the benzene ring survives and the side chain is cut down to −COOH.
Identifying (A) …
Method: Functional Group & Reaction Mapping with Degradation Analysis
This method identifies unknown organic compounds by:
- Mapping chemical tests to deduce functional groups.
- Using molecular formula changes in oxidation to confirm structure.
Step 1: Analyse the molecular formula of (A) — C8H8O
- Degree of unsaturation (DoU) formula:
DoU=22C+2−H=22(8)+2−8=210=5
→ 5 units of unsaturation.
- 1 from the C=O group (likely).
- 4 from a benzene ring (since 4 DoU = one ring + 3 double bonds). → So (A) is an aromatic carbonyl compound.
Step 2: Interpret the chemical tests
| Test | Observation | Inference |
|---|---|---|
| 2,4-DNP | Orange-red precipitate | Carbonyl group (aldehyde or ketone) present. |
| Iodoform test (I₂ + NaOH) | Yellow precipitate (CHI₃) | Methyl ketone (−COCHX3) or ethanol type — but here it's a ketone. |
| Tollens’ / Fehling’s | No reduction | Not an aldehyde — so (A) is a ketone. |
| Br₂ water / Baeyer’s | No decolourisation | No C=C double bond — so the only unsaturation is from the ring and C=O. |
Conclusion so far: (A) is an aromatic methyl ketone — i.e., a benzene ring with a −COCHX3 group.
Step 3: Use the oxidation product (B) to fix the exact structure
- Drastic oxidation with chromic acid (HX2CrOX4) converts (A) to (B): C7H6O2. …
🧠 Step 1: Understand the clues before jumping
| Clue | What it tells you |
|---|---|
| Formula C8H8O | Degree of unsaturation = 5 (likely aromatic + one C=O) |
| Orange-red precipitate with 2,4-DNP | Carbonyl group (aldehyde or ketone) present |
| Yellow precipitate with I2/NaOH (iodoform test +ve) | Methyl ketone (CH3CO−) or ethanol/ secondary alcohol with CH3CH(OH)− |
| Does not reduce Tollens’/Fehling’s | Not an aldehyde → must be a ketone |
| Does not decolourise Br₂ water / Baeyer’s | No C=C (no alkene) |
| Drastic oxidation with chromic acid → C7H6O2 | That’s benzoic acid (C6H5COOH) → one carbon lost as CO2 |
Conclusion: (A) is a methyl ketone with a benzene ring — specifically acetophenone (C6H5COCH3).
✗ Common Mistake #1: Ignoring the iodoform test implication
What students do wrong:
They see “orange-red precipitate with 2,4-DNP” and immediately assume it’s an aldehyde. Then they get stuck because it doesn’t reduce Tollens’.
How to avoid:
- 2,4-DNP is not specific — it reacts with any carbonyl (aldehyde or ketone).
- The iodoform test is the key: a yellow precipitate means a methyl ketone (CH3CO−) or a secondary alcohol with CH3CH(OH)− (which would oxidise to a methyl ketone).
- Since it doesn’t reduce Tollens’, it must be a ketone.
✓ Rule: Always pair 2,4-DNP with Tollens’/Fehling’s to distinguish aldehyde vs ketone.
✗ Common Mistake #2: Misinterpreting the oxidation product
What students do wrong:
They see C7H6O2 and think “benzoic acid” but forget to check the carbon count — starting with 8 carbons, ending with 7 means one carbon was lost as CO2.
How to avoid:
- Drastic oxidation of a methyl ketone (RCOCH3) with chromic acid cleaves the C−COCH3 bond, giving RCOOH + CO2.
- Here R=C6H5 (phenyl), so product is C6H5COOH (benzoic acid).
- Count carbons: C6H5COCH3 (8C) → C6H5COOH (7C) + CO2 (1C). Perfect match.
✓ Rule: For methyl ketones, drastic oxidation always loses the methyl carbon as CO2.
✗ Common Mistake #3: Forgetting to check unsaturation
What students do wrong:
They propose a structure like C6H5CH2CHO (phenylacetaldehyde) — but that’s an aldehyde (would reduce Tollens’) and has 8 carbons but wrong unsaturation.
How to avoid:
- Calculate degree of unsaturation (DU) for C8H8O:
DU=22C+2−H=216+2−8=5
- A benzene ring accounts for 4, one C=O accounts for 1 → total 5.
- So no room for an extra double bond or ring.
- This rules out any alkene or additional ring.
✓ Rule: Always compute DU before proposing a structure — it’s a powerful filter.
✗ Common Mistake #4: Confusing “drastic” vs “mild” oxidation
What students do wrong: …
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