Q.CH3CH2OH can be converted into CH3CHO by ____________.
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Alcohol Oxidation
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 (acidified potassium dichromate): oxidizes 1° alcohols all the way to carboxylic acids; 2° alcohols to ketones. (Not to be confused with Jones reagent, which is specifically CrO₃ dissolved in dilute aqueous H₂SO₄, often used in acetone — a related but distinct oxidant with the same general 1°→acid / 2°→ketone outcome.) …
Why this formula?
Alcohol Oxidation: Why the Reactions Work the Way They Do
Alcohol oxidation is a fundamental reaction in organic chemistry, and understanding why it proceeds as it does is crucial for Indian board exams (Class 12, JEE, NEET). Let's break it down step-by-step.
1. The Core Idea: Loss of Hydrogen
Oxidation in organic chemistry means loss of hydrogen (or gain of oxygen). For alcohols, this happens at the carbon bearing the –OH group.
- Primary alcohol (R−CH2OH): Has two hydrogens on the carbon attached to –OH.
- Secondary alcohol (R2CHOH): Has one hydrogen on that carbon.
- Tertiary alcohol (R3COH): Has zero hydrogens on that carbon.
Key insight: The number of hydrogens on the carbon with –OH determines if and how far oxidation can go.
2. Why Primary Alcohols Give Aldehydes (Then Carboxylic Acids)
Step 1: Aldehyde formation
When a primary alcohol (R−CH2OH) is oxidized, the first product is an aldehyde (R−CHO).
Why? The oxidizing agent (like K2Cr2O7 / H2SO4 or PCC) removes two hydrogens:
- One from the –OH group
- One from the carbon atom
The carbon–oxygen bond becomes a double bond (C=O), forming the aldehyde.
R−CH2OH[O]R−CHO+H2O
But why stop here? The aldehyde still has one hydrogen on the carbonyl carbon. If a strong oxidant is present, it can remove that hydrogen too.
Step 2: Carboxylic acid formation
With excess strong oxidant (e.g., K2Cr2O7 / H2SO4, heat), the aldehyde is further oxidized to a carboxylic acid (R−COOH).
R−CHO[O]R−COOH
Why does this happen? The aldehyde's carbonyl carbon is electrophilic (partially positive). Water (from the reaction medium) adds to it, forming a gem-diol intermediate. The oxidant then removes two more hydrogens, giving the acid.
Exam tip: To stop at the aldehyde, use a mild oxidant like PCC (pyridinium chlorochromate) in anhydrous conditions — no water means no gem-diol formation.
3. Why Secondary Alcohols Give Ketones (and Stop)
A secondary alcohol (R2CHOH) has only one hydrogen on the carbon with –OH. Oxidation removes:
- One hydrogen from –OH
- One hydrogen from the carbon
This forms a ketone (R2C=O).
R2CHOH[O]R2C=O+H2O
Why does it stop here? The ketone has no hydrogen on the carbonyl carbon. Without that hydrogen, further oxidation (under normal conditions) is impossible — you'd need to break a C−C bond, which requires much harsher conditions.
Key result: Secondary alcohols cannot be oxidized further than ketones under standard conditions.
4. Why Tertiary Alcohols Do NOT Oxidize
A tertiary alcohol (R3COH) has zero hydrogens on the carbon bearing –OH.
What happens if you try? The oxidant cannot remove any hydrogen from that carbon. The only possible reaction would be breaking a C−C bond, which doesn't happen under normal oxidation conditions.
Result: Tertiary alcohols are resistant to oxidation under mild to moderate conditions. They require strong heating with powerful oxidants (like K2Cr2O7 / H2SO4, heat) to break carbon–carbon bonds — this is destructive oxidation, not useful for synthesis.
5. The "Why" in One Table
| Alcohol Type | Hydrogens on C–OH | Product | Why? |
|---|---|---|---|
| Primary (1∘) | 2 | Aldehyde → Carboxylic acid | Two hydrogens available; aldehyde still has one more |
The key idea is Alcohol Oxidation — specifically, the controlled oxidation of a primary alcohol to an aldehyde without over-oxidising to the carboxylic acid.
- CH3CH2OH (ethanol) is a primary alcohol. To get CH3CHO (acetaldehyde), we need an oxidising agent that stops at the aldehyde stage.
- Catalytic hydrogenation and LiAlH4 are reducing agents — they would convert ethanol to ethane or keep it as alcohol, not oxidise it.
- KMnO4 is a strong oxidant — it would directly oxidise ethanol all the way to acetic acid (CH3COOH), not stop at the aldehyde. …
The conversion of ethanol (CH3CH2OH) to acetaldehyde (CH3CHO) is a controlled oxidation reaction. The correct reagent is pyridinium chlorochromate (PCC), which selectively oxidizes primary alcohols to aldehydes without over-oxidation to carboxylic acids. The answer is (iii).
The question asks for a method to convert ethanol into acetaldehyde. This is a classic example of partial oxidation of a primary alcohol. The key challenge is to stop the oxidation at the aldehyde stage, not push it all the way to the carboxylic acid (acetic acid, CH3COOH).
Let's think about what each option does.
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Catalytic hydrogenation (Option (i)) adds hydrogen across double or triple bonds. Ethanol has no such bonds — it's already saturated. Hydrogenation would not change it. This is a reduction process, not an oxidation. So this is wrong.
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Treatment with LiAlH4 (Option (ii)) is a powerful reducing agent. It reduces carbonyl compounds (aldehydes, ketones, acids) back to alcohols. Using it on ethanol would do nothing — ethanol is already at the alcohol oxidation level. This is the opposite of what we need. So this is wrong.
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Treatment with pyridinium chlorochromate (PCC) (Option (iii)) is a mild oxidizing agent specifically designed for this job. PCC in anhydrous conditions (usually in dichloromethane, CH2Cl2) oxidizes primary alcohols to aldehydes and stops there. It does not have water present to hydrate the aldehyde, so no further oxidation to the carboxylic acid occurs. This is the correct choice. …
Method: Controlled Oxidation of Primary Alcohols
The concept here is that a primary alcohol (CH3CH2OH, ethanol) can be oxidised to an aldehyde (CH3CHO, ethanal) only if the oxidising agent is mild and the reaction is stopped before further oxidation to a carboxylic acid occurs.
Steps to identify the correct reagent:
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Recognise the functional group change
- Starting material: Primary alcohol (−OH on a terminal carbon).
- Product: Aldehyde (−CHO).
- This is a two-electron oxidation (loss of two hydrogen atoms).
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Eliminate reducing agents
- Catalytic hydrogenation (A) and LiAlH4 (B) are reducing agents — they would convert an aldehyde back to an alcohol, not oxidise it.
- ✗ (A) and (B) are incorrect.
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Distinguish between strong and mild oxidants
- KMnO4 (D) is a strong oxidant. It will over-oxidise a primary alcohol all the way to a carboxylic acid (CH3COOH), not stop at the aldehyde.
- ✗ (D) is incorrect.
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Identify the mild, selective oxidant …
Here are the common mistakes students make on this question, along with how to avoid each.
Mistake 1: Confusing Oxidation with Reduction
- The Error: Choosing (A) catalytic hydrogenation or (B) treatment with LiAlH4.
- Why it happens: Students see a conversion and forget to check whether the carbon is gaining or losing oxygen/hydrogen. They might recall that LiAlH4 is a strong "reagent" without remembering its function.
- How to avoid: Always check the oxidation state of the carbon attached to the -OH group.
- In CH3CH2OH (ethanol), the carbon has one bond to oxygen.
- In CH3CHO (acetaldehyde), the carbon has a double bond to oxygen.
- Moving from a single bond to a double bond with oxygen is oxidation (loss of hydrogen).
- Catalytic hydrogenation (H2/catalyst) and LiAlH4 are reducing agents. They add hydrogen, which would turn an aldehyde back into an alcohol. They cannot perform the oxidation needed here.
Mistake 2: Overlooking the "Mild vs. Strong" Oxidizer
- The Error: Choosing (D) treatment with KMnO4.
- Why it happens: Students know KMnO4 is an oxidising agent, so they assume it will work. They forget that strong oxidisers do not stop at the aldehyde stage.
- How to avoid: Memorise the selectivity of common oxidising agents.
- Mild oxidisers (like PCC – pyridinium chlorochromate) stop at the aldehyde.
- Strong oxidisers (like acidic KMnO4 or K2Cr2O7) will over-oxidise a primary alcohol all the way to a carboxylic acid (CH3COOH).
- Therefore, KMnO4 would give CH3COOH, not CH3CHO.
Mistake 3: Not Knowing the Specific Reagent (PCC)
- The Error: Not recognising option (C) as the correct answer. …
Showing the 12 most recent of 16 on this concept.
- KCET 2026Set D31 markMCQQ.$C_4H_8 \xrightarrow{\text{(i) (BH}_3\text{)}_2\text{,(ii) } H_2O_2/NaOH} P \xrightarrow{CrO_3,\ \text{anhydrous medium}} Q \xrightarrow{\text{(i) } CH_3MgBr,\ \text{(ii) } H_3O^+} R + Mg(OH)Br.TheorganiccompoundsP,QandRare(A)P = CH_3\text{-}CH(OH)\text{-}CH_2\text{-}CH_3,Q = CH_3\text{-}C(=O)\text{-}CH_3,R = CH_3\text{-}C(OH)(CH_3)\text{-}CH_2\text{-}CH_3(B)P = CH_3\text{-}CH_2\text{-}CH_2\text{-}OH,Q = CH_3\text{-}CH_2\text{-}CHO,R = CH_3\text{-}CH_2\text{-}CH(OH)\text{-}CH_3(C)P = CH_3\text{-}CH_2\text{-}CH_2\text{-}OH,Q = CH_3\text{-}CH_2\text{-}COOH,R = CH_3\text{-}CH_2\text{-}C(=O)\text{-}OCH_3(D)P = CH_3\text{-}CH(OH)\text{-}CH_3,Q = CH_3\text{-}C(=O)\text{-}CH_3,R = CH_3\text{-}CH(OCH_3)\text{-}CH_3$
›Reveal solutionSolution
Identify but-2-ene as the alkene, then trace it through hydroboration-oxidation, an anhydrous CrO3 oxidation, and a Grignard addition.
Step 1 — Hydroboration-oxidation of but-2-ene
But-2-ene (CH3-CH=CH-CH3) is a symmetric alkene, so (BH3)2 addition followed by H2O2/NaOH (anti-Markovnikov, syn addition) gives the same product from either end: butan-2-ol, P=CH3-CH(OH)-CH2-CH3 — a secondary alcohol.
Step 2 — Oxidation with CrO3 in anhydrous medium
CrO3 under anhydrous conditions oxidizes a secondary alcohol cleanly to a ketone (it cannot over-oxidize further, since there's no α-hydrogen loss pathway to a carboxylic acid for a secondary alcohol). P is oxidized to butan-2-one, Q=CH3-C(=O)-CH2-CH3, matching the option's CH3-C(=O)-CH3 shorthand for the ketone core.
Step 3 — Grignard addition …
- KCET 2025Set D-41 markMCQQ.The organometallic compound (CH3)3CMgBr on reaction with D2O produces __________ (A) (CH3)3COD (B) (CD3)3CD (C) (CD3)3COD (D) (CH3)3CD
›Reveal solutionSolution
The Grignard carbon is a carbanion; D2O protonates (deuterates) it, so the C–MgBr bond simply becomes a C–D bond.
Step 1 — The polarity of the Grignard reagent.
In (CH3)3C−MgBr, carbon (EN ≈2.5) is far more electronegative than magnesium (EN ≈1.2). The C–Mg bond is therefore strongly polarised:
(CH3)3Cδ−−Mgδ+Br
The tert-butyl carbon carries substantial negative charge — it behaves as a carbanion, (CH3)3C−. Carbanions are both strong nucleophiles and very strong bases (the conjugate base of an alkane, pKa≈50).
Step 2 — Why D2O reacts at all.
Against a base that strong, water is a perfectly good acid. Heavy water D2O is chemically identical to H2O except that its exchangeable hydrogens are the isotope deuterium. The reaction is a simple, extremely fast acid–base proton (deuteron) transfer:
(CH3)3C−MgBr+D2O⟶(CH3)3C−D+Mg(OD)Br
The carbanion takes a D+ from D2O; the OD− left behind pairs with the magnesium.
Step 3 — Which position gets the deuterium.
Only one deuterium is delivered, and only to the carbon that previously held the MgBr — the quaternary-becoming tert-butyl carbon. The nine hydrogens of the three CH3 groups are ordinary, non-acidic C–H bonds; they are not exchangeable and remain as H.
So the product is (CH3)3C−D — 2-deuterio-2-methylpropane.
Step 4 — Rejecting the distractors. …
- COMEDK 2025Set 2025-A1 markMCQQ.Identify X and Y formed in the following two reactions.(i) Decan-1-ol Jones reagent X (ii). Sodium salt of XNaOH/CaO,ΔY (A) A. X= Decanoic acid Y= Nonane (B) X= Octanoic acid Y= Heptane. (C) X=1− Methoxy nonane Y= Octane. (D) X= Decan-2-one Y= Octane.
›Reveal solutionSolution
Jones reagent oxidises a primary alcohol to a carboxylic acid, and the sodium salt of that acid undergoes decarboxylation with soda lime to give an alkane with one fewer carbon. Here, decan-1-ol → decanoic acid (X) → nonane (Y), so option (A) is correct.
Concept & Intuition
The problem tests two classic organic reactions in sequence. First, Jones reagent (chromic acid in acetone) is a strong oxidant that converts primary alcohols all the way to carboxylic acids — it does not stop at the aldehyde. Second, heating the sodium salt of a carboxylic acid with soda lime (NaOH/CaO) causes decarboxylation: the –COONa group is replaced by a hydrogen atom, producing an alkane with one fewer carbon atom. So the carbon chain shrinks by one in the second step. Starting from a C10 alcohol, we expect a C10 acid, then a C9 alkane.
Step-by-step reasoning
- Identify the starting material Decan-1-ol is a straight-chain primary alcohol with 10 carbons:
CH3(CH2)8CH2OH
- First reaction: Jones reagent Jones reagent (CrO3/H2SO4 in acetone) oxidises primary alcohols to carboxylic acids. The alcohol group –CH₂OH becomes –COOH. No carbon atoms are lost or gained.
CH3(CH2)8CH2OHJonesCH3(CH2)8COOH
This product is decanoic acid (C10 carboxylic acid). So X = decanoic acid.
- Second reaction: Decarboxylation with soda lime The sodium salt of X is first formed (by treating the acid with NaOH), then heated with soda lime (NaOH/CaO). This is the classic decarboxylation reaction:
RCOONa+NaOHCaO,ΔR−H+Na2CO3
Here R = CH3(CH2)8– (a C9 chain). The –COONa group is replaced by H, giving an alkane with one fewer carbon:
CH3(CH2)8H=CH3(CH2)7CH3
That is nonane (C9H20). So Y = nonane.
- Match with options …
- COMEDK 2025Set 2025-E1 markMCQQ.Identify [X] used in the given reaction. [X]+ Copper /573 K→[Y] $[\mathrm{Y}] \xrightarrow[\text {(ii) } \mathrm{H}_2 \mathrm{O} / \mathrm{H}^{+}]{\text {(i) } \mathrm{CH}_3 \mathrm{MgBr}}$ Tert.butyl alcohol. (major product) (A) Propan-1-ol (B) Butan-1-ol (C) Propan-2-ol (D) Butan-2-ol
›Reveal solutionSolution
The key is to work backwards from the final product (tert-butyl alcohol) through the Grignard reaction to identify the aldehyde/ketone [Y], then deduce the alcohol [X] that dehydrates to give [Y] over copper at 573 K. The correct starting material is propan-2-ol, option (C).
We are given a two-step reaction sequence. The final product is tert-butyl alcohol (2-methylpropan-2-ol). We need to identify the starting alcohol [X].
Concept & Intuition
The reaction of [X] with copper at 573 K is a classic dehydrogenation of an alcohol to a carbonyl compound (aldehyde or ketone). Then, that carbonyl compound [Y] reacts with methylmagnesium bromide (CH₃MgBr) followed by acidic hydrolysis — a Grignard reaction — to give an alcohol. Since the final product is a tert-butyl alcohol (a tertiary alcohol with four carbons), [Y] must be a ketone that, when attacked by one methyl group from the Grignard reagent, yields that tertiary alcohol. Working backwards: tert-butyl alcohol has the structure (CH₃)₃COH. Removing one methyl group (the one added by the Grignard) gives acetone, CH₃COCH₃. So [Y] is acetone. Now, which alcohol [X] gives acetone upon dehydrogenation over copper at 573 K? That is propan-2-ol (isopropyl alcohol), which loses two hydrogens to become acetone.
Let’s verify step by step.
- Identify [Y] from the final product
The Grignard reaction: a carbonyl compound [Y] reacts with CH₃MgBr, then H₂O/H⁺, to give an alcohol.
- If [Y] is an aldehyde (RCHO), the product is a secondary alcohol.
- If [Y] is a ketone (RCOR'), the product is a tertiary alcohol (if both R and R' are not H). Here the product is tert-butyl alcohol, (CH₃)₃COH. This is a tertiary alcohol with three methyl groups attached to the carbon bearing the –OH. The Grignard reagent adds one methyl group. So the carbonyl [Y] must have the other two methyl groups already attached: that is acetone, CH₃COCH₃. Reaction:
CH3COCH3+CH3MgBr→(CH3)3C−OMgBrH2O/H+(CH3)3COH
So [Y] = acetone.
- Identify [X] from the dehydrogenation step The reaction:
[X]+Copper/573 K→[Y]
Copper at 573 K (about 300 °C) is a catalyst for dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones.
- A primary alcohol gives an aldehyde.
- A secondary alcohol gives a ketone. …
- Identify [Y] from the final product
The Grignard reaction: a carbonyl compound [Y] reacts with CH₃MgBr, then H₂O/H⁺, to give an alcohol.
- KCET 2024Set B-21 markMCQQ.Biologically active adrenaline and ephedrine used to increase blood pressure contain: (A) Primary amino group (B) Secondary amino group (C) Tertiary amino group (D) Quaternary ammonium salt
›Reveal solutionSolution
Both molecules contain an −NH−CH3 (N-methylamino) group — nitrogen attached to two carbons — which is by definition a secondary amine.
1. The concept — how amines are classified.
Amines are classified by the number of carbon atoms bonded to the nitrogen (not by the carbon skeleton, as with alcohols):
- Primary (1∘): R−NH2 — one C on N.
- Secondary (2∘): R−NH−R′ — two C's on N.
- Tertiary (3∘): R3N — three C's on N.
- Quaternary ammonium salt: R4N+X− — four C's on N, positively charged.
2. Look at the two molecules.
- Adrenaline (epinephrine): a catechol ring bearing a −CH(OH)−CH2−NH−CH3 side chain. The nitrogen is bonded to the side-chain CH2 and to a CH3 group ⇒ two carbons on N.
- Ephedrine: a benzene ring with a −CH(OH)−CH(CH3)−NH−CH3 side chain. Again the nitrogen carries the side-chain carbon and an N-methyl group ⇒ two carbons on N. …
- KCET 2024Set B-21 markMCQQ.Which one of the following pairs will show positive deviation from Raoult’s Law? (A) Water - HCl (B) Benzene - Methanol (C) Water - HNO3 (D) Acetone - Chloroform
›Reveal solutionSolution
Positive deviation happens when mixing weakens the intermolecular forces — benzene breaks up methanol's hydrogen bonds, so the mixture is more volatile than Raoult's law predicts.
Step 1 — The criterion for positive deviation
For an ideal solution the A–B interaction is the same strength as A–A and B–B. Deviations arise when it is not:
A–B interaction Escaping tendency pobs vs Raoult ΔHmix ΔVmix Positive deviation weaker than A–A, B–B increases pobs>pRaoult >0 (endothermic) >0 Negative deviation stronger than A–A, B–B decreases pobs<pRaoult <0 (exothermic) <0 So the question reduces to: in which pair does mixing destroy interactions rather than create them?
Step 2 — Test option (B): benzene + methanol ✓
Pure methanol (CH3OH) molecules are held together by a strong network of hydrogen bonds (O−H⋯O). Pure benzene is a non-polar hydrocarbon held by weak London forces, and it can form no hydrogen bond with methanol.
When benzene is added, its molecules wedge between the methanol molecules and break the H-bond network. The resulting methanol–benzene interaction is far weaker than the methanol–methanol hydrogen bonding it replaced. Freed from their H-bonds, the methanol molecules escape into the vapour more easily:
pobs>xApA∘+xBpB∘
Energy must be supplied to break those H-bonds, so ΔHmix>0 and the volume expands, ΔVmix>0 — the full signature of positive deviation. ✓
Step 3 — Why the other three show negative deviation …
- KCET 2023Set D-21 markMCQQ.Which of the following compound does not give dinitrogen on heating? (A) Ba(N3)2 (B) NH4NO2 (C) NH4NO3 (D) (NH4)2Cr2O7
›Reveal solutionSolution
Write the thermal decomposition of each salt and look for the one whose nitrogen leaves as N2O rather than N2.
Step 1 — Why these salts give N2 at all
Each of the first, second and fourth choices contains nitrogen in two different oxidation states (or an intrinsically unstable N–N–N chain). On heating, an internal redox reaction occurs in which the oxidised and reduced nitrogen atoms meet at the stable oxidation state 0, i.e. N2. This is exactly how dinitrogen is prepared in the laboratory.
Step 2 — Test each option
(A) Barium azide — the azide ion is thermodynamically unstable with respect to N2:
Ba(N3)2ΔBa+3N2↑
This is the route to very pure dinitrogen. Gives N2.
(B) Ammonium nitrite — N is −3 in NH4+ and +3 in NO2−; they comproportionate to 0:
NH4NO2ΔN2↑+2H2O
This is the standard laboratory preparation of N2. Gives N2.
(D) Ammonium dichromate — N is −3, Cr is +6; the chromium(VI) oxidises the ammonium nitrogen:
(NH4)2Cr2O7ΔN2↑+Cr2O3+4H2O …
- KCET 2023Set D-21 markMCQQ.Which one of the following oxoacids of phosphorus can reduce AgNO3 to metallic silver? (A) H3PO2 (B) H4P2O7 (C) H4P2O6 (D) H3PO4
›Reveal solutionSolution
The reducing power of an oxoacid of phosphorus depends on the presence of P–H bonds. Only hypophosphorous acid (H3PO2) has two P–H bonds, making it a strong enough reductant to reduce AgNO3 to metallic silver. The correct option is (A).
The key concept here is that the reducing ability of phosphorus oxoacids is directly linked to the number of P–H bonds in their structure. Phosphorus in these acids is typically in a positive oxidation state, but when it is bonded directly to hydrogen, those hydrogens can be released as reducing equivalents. The more P–H bonds, the stronger the reducing agent.
Silver nitrate (AgNO3) is a classic oxidizing agent — silver ions (Ag+) get reduced to metallic silver (Ag) when they accept electrons. So we need an oxoacid that can donate electrons readily. Let’s examine each option.
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Option (A): H3PO2 (hypophosphorous acid)
Its structure is H–P(=O)(OH)2, but the key detail is that two hydrogens are directly bonded to phosphorus, not to oxygen. So it has two P–H bonds. Phosphorus here is in the +1 oxidation state. These P–H bonds are easily broken, releasing hydrogen as H− (hydride-like) or as reducing equivalents. This makes H3PO2 a strong reducing agent — it can reduce Ag+ to Ag.
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Option (B): H4P2O7 (pyrophosphoric acid)
This is a dimeric acid formed by condensation of two H3PO4 molecules. Its structure has no P–H bonds — all hydrogens are attached to oxygen. Phosphorus is in the +5 oxidation state. Without P–H bonds, it has negligible reducing power. It cannot reduce AgNO3.
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Option (C): H4P2O6 (hypophosphoric acid)
This acid has a P–P bond, but no P–H bonds. The oxidation state of each phosphorus is +4. While it can act as a mild reducing agent in some contexts (due to the P–P bond), it is not strong enough to reduce Ag+ to silver under normal conditions. The classic reducing oxoacids are those with P–H bonds.
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Option (D): H3PO4 (orthophosphoric acid) …
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- KCET 2023Set D-21 markMCQQ.CH3–CH=CH–CH2OH PCC CH3–CH=CH–CHO Hybridisation change involved at C–1 in the above reaction (A) sp3 to sp (B) sp3 to sp2 (C) sp2 to sp3 (D) sp to sp2
›Reveal solutionSolution
The reaction is a mild oxidation of a primary allylic alcohol to an aldehyde using PCC. At C‑1, the carbon changes from sp3 hybridised (in the alcohol) to sp2 hybridised (in the aldehyde). The correct option is (B).
The key here is to recognise what PCC does and what happens to the carbon that bears the –OH group. PCC (pyridinium chlorochromate) is a mild oxidising agent that converts primary alcohols to aldehydes without over‑oxidising to carboxylic acids. It does not touch carbon‑carbon double bonds. So the rest of the molecule — the CH₃–CH=CH– part — stays exactly as it is.
The carbon we care about is C‑1, the one that originally holds the –OH. In the starting alcohol, that carbon is bonded to three other atoms (two hydrogens and the next carbon) plus the oxygen of the –OH. That’s four sigma bonds, so it is sp3 hybridised. After oxidation, that same carbon becomes part of a carbonyl group (C=O). Now it has a double bond to oxygen and a single bond to hydrogen and to the next carbon — only three sigma bonds and one pi bond. That geometry is trigonal planar, which means sp2 hybridisation.
So the change is from sp3 to sp2.
Let’s walk through it step by step.
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Identify the carbon in question. The problem says “hybridisation change involved at C‑1”. In the given structure CH₃–CH=CH–CH₂OH, the carbon chain is numbered from the alcohol end: C‑1 is the –CH₂OH carbon. That’s the one that gets oxidised.
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Hybridisation of C‑1 in the reactant. In CH₃–CH=CH–CH₂OH, C‑1 is bonded to two H atoms, one C atom (C‑2), and one O atom (from –OH). That’s four sigma bonds, no pi bonds. Four sigma bonds → tetrahedral geometry → sp3 hybridisation.
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What happens in the reaction. PCC oxidises the primary alcohol (–CH₂OH) to an aldehyde (–CHO). The –OH group loses two hydrogen atoms (one from the O–H and one from the C–H), forming a C=O double bond. The rest of the molecule, including the C=C double bond between C‑2 and C‑3, remains unchanged. …
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- COMEDK 2023Set 2023-M1 markMCQQ.Which of the following is incorrect? (A) Primary alcohols are very easily oxidised to aldehydes, which are oxidised to acids with same number of C-atoms. (B) Secondary alcohols are very easily oxidised to ketones, which are oxidised to acids with same number of C-atoms. (C) Secondary alcohols are easily oxidised to ketones, which are oxidised to acids with lesser number of C-atoms. (D) Secondary and tertiary alcohols on oxidation form acids with lesser number of C-atoms.
›Reveal solutionSolution
Oxidation of a ketone (from a 2∘ alcohol) breaks a C–C bond and gives acids with fewer carbons, so statement (B) claiming the same number of C-atoms is wrong.
Oxidation behaviour of alcohols:
- Primary alcohols oxidise to aldehydes, which further oxidise to carboxylic acids with the same number of carbon atoms (the –CH2OH carbon becomes –COOH). So (A) is correct.
- Secondary alcohols oxidise to ketones. A ketone can only be oxidised further under vigorous conditions, and this cleaves a C–C bond, giving carboxylic acids with fewer carbon atoms. So (C) and (D) are correct. …
- KCET 2022Set B-31 markMCQQ.In Carbylamine test for primary amines the resulting foul smelting product is (A) CH3NC (B) COCl2 (C) CH3NCl2 (D) CH3CN
›Reveal solutionSolution
The carbylamine test converts a 1° amine into a foul-smelling isocyanide (R–NC), so the product here is methyl isocyanide, CH3NC.
Step 1 — The test.
Heating a primary amine with chloroform and alcoholic potassium hydroxide gives an isocyanide (carbylamine):
R−NH2+CHCl3+3KOH Δ R−NC+3KCl+3H2O
For methylamine (R=CH3):
CH3NH2+CHCl3+3KOH⟶CH3NC+3KCl+3H2O
Step 2 — Why it works (the mechanism in one line).
Alcoholic KOH deprotonates chloroform to CCl3−, which loses Cl− to give the electron-deficient dichlorocarbene, :CCl2. The amine's nitrogen lone pair attacks this carbene; two successive eliminations of HCl then leave the carbon triple-bonded to nitrogen through the nitrogen's lone pair — an isocyanide, R−N+≡C−.
Step 3 — Why it is a test.
Only a primary amine has the two N–H hydrogens needed for the double dehydrohalogenation. Secondary and tertiary amines do not give the reaction, so the appearance of the nauseating isocyanide smell is a positive identification of a 1° amine. (Being both diagnostic and unpleasant, this reaction is done only in small quantities in a fume cupboard.)
Step 4 — Reject the other options. …
- KCET 2022Set B-31 markMCQQ.Amphoteric oxide among the following: (A) Ag2O (B) SnO2 (C) BeO (D) CO2
›Reveal solutionSolution
Test each oxide against both an acid and an alkali; the one that reacts with both is amphoteric — BeO.
Step 1 — What "amphoteric" means.
An amphoteric oxide reacts with acids (behaving as a base) and with alkalis (behaving as an acid), giving a salt and water in each case. Metal oxides are usually basic and non-metal oxides acidic; amphoteric character appears at the metal/non-metal borderline (Be, Al, Zn, Sn, Pb, Ga...).
Step 2 — Screen the options.
- (A) Ag2O — a basic oxide of a noble metal: Ag2O+2HNO3→2AgNO3+H2O, but it does not dissolve in NaOH to give an argentate. ✗
- (D) CO2 — the standard acidic (anhydride) oxide: CO2+2NaOH→Na2CO3+H2O, no reaction with acid. ✗
- (C) BeO — reacts both ways: BeO+2HCl→BeCl2+H2O(base-like) …
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