100+ direct NCERT questions from Haloalkanes, Alcohols & Phenols, Carbonyl Compounds, Amines & Biomolecules — click an option to reveal the answer.
🧪 Haloalkanes & Haloarenes 6 marks
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Q1
The C–X bond in haloalkanes is polar because:
Correct: B. Halogens (F, Cl, Br, I) are more electronegative than carbon, making the C–X bond polar covalent with δ+ on C and δ− on X. This polarity is responsible for the nucleophilic substitution and elimination reactions of haloalkanes. Bond polarity decreases in the order C–F > C–Cl > C–Br > C–I. Bond strength also decreases: C–F > C–Cl > C–Br > C–I, but reactivity increases (C–I most reactive) because bond enthalpy is more important than polarity for reactivity.
Q2
In an SN2 reaction, the nucleophile attacks:
Correct: C — Backside attack. In SN2 (bimolecular nucleophilic substitution), the nucleophile attacks the α-carbon from the side opposite to the leaving group. This results in Walden inversion (umbrella inversion of configuration). The reaction is a single-step, concerted mechanism with a trigonal bipyramidal transition state. Rate = k[substrate][nucleophile]. Favoured by primary substrates, strong nucleophiles, polar aprotic solvents (DMSO, acetone). Steric hindrance severely retards SN2.
Q3
SN1 reaction proceeds through:
Correct: A — Carbocation intermediate. SN1 is a two-step mechanism: (1) ionisation of C–X bond to form carbocation (rate-determining step), (2) nucleophile attacks carbocation from both faces → racemisation. Rate = k[substrate] only. Favoured by 3° > 2° > 1° substrates (carbocation stability), polar protic solvents (water, alcohol stabilise ions), and weak nucleophiles. Example: (CH₃)₃CBr + H₂O → (CH₃)₃COH. Rearrangements possible via carbocation.
Q4
The order of reactivity of alkyl halides in SN2 reaction is:
Correct: D — CH₃X > 1° > 2° > 3°. SN2 reactivity decreases as steric hindrance increases. Methyl halide (no alkyl groups) is least hindered → fastest SN2. Tertiary halide has three bulky alkyl groups blocking backside attack → virtually no SN2. Contrast with SN1 where tertiary is fastest (most stable carbocation). This is the key difference: SN2 favours least hindered, SN1 favours most substituted (most stable carbocation).
Q5
Grignard reagent (RMgX) reacts with water to give:
Correct: B — Alkane + MgX(OH). Grignard reagent (RMgX) is prepared from alkyl halide + Mg metal in dry ether. The C–Mg bond is highly polar (Cδ⁻–Mg δ+), making R⁻ a powerful nucleophile and strong base. Reaction with water (proton source): RMgX + H₂O → R–H + Mg(OH)X. This is why Grignard reactions must be done in strictly anhydrous conditions. Grignard reagents react with CO₂ → carboxylic acids; with HCHO → 1° alcohol; with RCHO → 2° alcohol; with R₂CO → 3° alcohol.
Q6
Which reagent converts an alkyl chloride to alkyl iodide via a halogen exchange reaction?
Correct: C — Finkelstein reaction. R–Cl + NaI (dry acetone) → R–I + NaCl↓. The reaction is driven to completion because NaCl is insoluble in acetone and precipitates out. This is an SN2 reaction where I⁻ is the nucleophile. The Swarts reaction converts alkyl chloride/bromide to fluoride using AgF or CoF₂: R–Cl + AgF → R–F + AgCl. KBr in water would not displace Cl⁻ favourably. NaI in acetone is the classic Finkelstein reagent.
Q7
Chlorobenzene is less reactive towards nucleophilic substitution than chloroalkanes because:
Correct: A — Resonance gives partial double bond character to C–Cl. In chlorobenzene, the lone pair of Cl overlaps with the π system of the ring, giving the C–Cl bond some double bond character (shorter and stronger than in alkyl chloride). The C–Cl bond length in chlorobenzene (169 pm) < that in alkyl chloride (177 pm). This, combined with the sp² carbon being less amenable to nucleophilic attack, makes haloarenes far less reactive. Nucleophilic aromatic substitution requires very strong nucleophiles (e.g., NaNH₂ at 300°C or presence of strong electron-withdrawing groups).
Q8
DDT (dichlorodiphenyltrichloroethane) was banned as a pesticide because:
Correct: D — Non-biodegradable, causes biomagnification. DDT was widely used as an insecticide (especially against malaria-causing mosquitoes) but is extremely stable in the environment. It accumulates in fatty tissues and undergoes biomagnification — concentrations increase up the food chain (plankton → fish → birds → humans). It causes eggshell thinning in birds (interferes with Ca metabolism), reproductive failure, and is a suspected carcinogen. It is an example of an environmental pollutant. BHC (benzene hexachloride) is another organochlorine pesticide with similar concerns.
Q9
Which of the following statements about optical activity of haloalkanes is correct?
Correct: B — Chiral carbon (asymmetric carbon) with four different substituents makes a compound optically active. Example: CH₃CHBrC₂H₅ has four different groups on C2 — optically active. SN2 gives Walden inversion (inversion of configuration, not racemisation). SN1 gives racemisation (carbocation is planar, attacked from both sides equally) — actually gives partial racemisation with slight predominance of inversion. An equimolar mixture of R and S enantiomers (racemic mixture) is optically inactive.
Q10
The reaction: CH₃CH₂Br + KOH(alc) → product. The major product is:
Correct: C — Ethene via E2 elimination. Alcoholic KOH (KOH dissolved in alcohol/ethanol) acts as a base and promotes elimination (E2). Aqueous KOH promotes substitution (SN2) to give alcohol. Mnemonic: alc. KOH → alkene (elimination); aq. KOH → alcohol (substitution). E2 is a bimolecular elimination: base removes β-H while leaving group departs simultaneously. For propyl and higher halides, Zaitsev's rule applies: the more substituted alkene (more stable) is the major product.
Q11
Freons (chlorofluorocarbons) are harmful because:
Correct: A — Cl• radicals destroy ozone layer. CFCs (e.g., CCl₂F₂, Freon-12) are used in refrigerants, aerosol propellants, and foam blowing. They are inert at ground level but in the stratosphere, UV radiation cleaves the C–Cl bond: CF₂Cl₂ → CF₂Cl• + Cl•. Chlorine radical then attacks ozone: Cl• + O₃ → ClO• + O₂; ClO• + O• → Cl• + O₂ (chain reaction, one Cl• can destroy ~10⁵ ozone molecules). The ozone layer (20–25 km altitude) absorbs harmful UV-B and UV-C radiation. Montreal Protocol (1987) phases out CFCs.
Q12
Which compound is formed when benzene diazonium chloride reacts with Cu₂Cl₂/HCl (Sandmeyer reaction)?
Correct: D — Chlorobenzene. Sandmeyer reaction: ArN₂⁺X⁻ + Cu₂X₂/HX → ArX + N₂. Specific reagents: Cu₂Cl₂/HCl → ArCl; Cu₂Br₂/HBr → ArBr; CuCN/KCN → ArCN. Gattermann reaction (alternative using Cu + HX or HCN directly) is less selective. Balz–Schiemann reaction: ArN₂⁺BF₄⁻ → ArF + BF₃ + N₂ (used to make aryl fluorides). Phenol is obtained when diazonium salt is hydrolysed with water (not Sandmeyer). These reactions allow introduction of halogens at positions not accessible by direct halogenation.
Q13
The boiling point of haloalkanes is higher than corresponding alkanes because:
Correct: B — Higher molecular mass + polar C–X bond. Replacement of H by halogen increases molecular mass significantly (Cl = 35, Br = 80, I = 127 vs H = 1), strengthening London dispersion forces. Additionally, the polar C–X bond introduces dipole-dipole interactions. Together these raise the boiling point. Haloalkanes cannot hydrogen bond with each other (no N–H or O–H). Among isomers, branching reduces bp (less surface area → weaker van der Waals). Density also increases: haloalkanes are denser than water except fluoroalkanes.
Q14
In the reaction of 2-bromobutane with NaOH(aq), the product formed via SN2 at the chiral centre is:
Correct: C — Inversion of configuration (Walden inversion). SN2 involves backside attack → the nucleophile (OH⁻) attacks from the face opposite to the leaving group (Br⁻). This causes inversion of the spatial arrangement at the chiral carbon. If the starting material is (R)-2-bromobutane, the product is (S)-2-butanol. This is called Walden inversion, named after Paul Walden who first observed it. Racemisation occurs in SN1 (planar carbocation intermediate). Retention occurs in some special reactions (not typical SN2).
Q15
Iodoform (CHI₃) test is positive for:
Correct: A — CH₃CO– group compounds and ethanol. Iodoform test (I₂/NaOH): yellow precipitate of CHI₃ (iodoform, antiseptic smell) is formed with compounds having CH₃CO– group (methyl ketones like acetone, methyl ethyl ketone) and with CH₃CH(OH)– or CH₃CHO group. Ethanol (CH₃CH₂OH) is oxidised to acetaldehyde first, then gives iodoform. Acetaldehyde (CH₃CHO) directly gives iodoform. Formaldehyde (HCHO) does not. Formic acid (HCOOH) does not. This test distinguishes acetaldehyde from other aldehydes and methyl ketones from other ketones.
Q16
Which of the following is a primary alkyl halide?
Correct: D — CH₃CH₂Br (bromoethane). Classification based on the number of carbon atoms directly attached to the carbon bearing the halogen: Primary (1°): one C attached — CH₃CH₂Br; Secondary (2°): two C attached — (CH₃)₂CHBr; Tertiary (3°): three C attached — (CH₃)₃CBr. C₆H₅Br is an aryl halide (not alkyl). Vinyl halide: CH₂=CHBr. Allyl halide: CH₂=CHCH₂Br. Classification determines the reaction mechanism: 3° → SN1; 1° → SN2; 2° → both (depending on conditions).
Q17
The reaction of alkyl halide with silver nitrite gives:
Correct: B — Nitroalkane (R–NO₂). AgNO₂ (silver nitrite) is an ambident nucleophile with both O and N nucleophilic sites. With AgNO₂, N attacks (ionic silver salt, N is more electronegative pathway favoured) → nitroalkane R–NO₂. With KNO₂/NaNO₂ (alkali metal nitrite), O attacks → alkyl nitrite R–O–N=O. Mnemonic: Silver = N-bonded product; Sodium/Potassium = O-bonded product. Similarly, CN⁻ is ambident: KCN gives nitrile (R–CN, C-attack); AgCN gives isonitrile (R–NC, N-attack).
Q18
Among CH₃F, CH₃Cl, CH₃Br, CH₃I — which has the highest boiling point?
Correct: C — CH₃I (iodomethane), bp = 42.4°C. As we go down the halogen group, molecular mass increases: CH₃F (34), CH₃Cl (51), CH₃Br (95), CH₃I (142). Higher molecular mass → stronger London dispersion forces → higher boiling point. Boiling points: CH₃F (−78°C) < CH₃Cl (−24°C) < CH₃Br (4°C) < CH₃I (42°C). Note: CH₃F has the most polar C–X bond but lowest bp because its small size means weak van der Waals forces dominate over polarity. C–F bond is very short and strong (highest bond energy among C–X bonds).
Q19
Gabriel phthalimide synthesis is used to prepare:
Correct: A — Pure primary amines. Gabriel synthesis: Phthalimide + KOH → potassium phthalimide (K⁺ salt) → alkylation with RX (SN2) → N-alkyl phthalimide → hydrolysis with aq. KOH or hydrazinolysis → primary amine (R–NH₂) + phthalic acid (or phthalhydrazide). Since only one alkyl group can be introduced (N has no H after first alkylation), only primary amines are produced — free from 2° and 3° contamination. Limitation: cannot be used for aromatic amines (aryl halides don't undergo SN2). Alternative for 1° amines: Hofmann bromamide degradation (from amides).
Q20
Which of the following undergoes nucleophilic substitution most readily?
Correct: C — Allyl chloride is most reactive, but among the options, allyl > n-propyl > vinyl > chlorobenzene. Actually allyl chloride (CH₂=CHCH₂Cl) is far more reactive than n-propyl chloride because the allyl carbocation/transition state is stabilised by resonance. Vinyl chloride (CH₂=CHCl) and chlorobenzene are least reactive (C–Cl has partial double bond character from conjugation/resonance). Order: allyl/benzyl >> 1° >> 2° >> 3° (for SN2); for SN1: tertiary > secondary > primary > allyl/benzyl (resonance-stabilised). Vinyl and aryl halides are practically inert to normal nucleophilic substitution.
🍺 Alcohols, Phenols & Ethers 8 marks
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Q1
Alcohols have higher boiling points than ethers and alkanes of comparable molecular mass because:
Correct: B — Hydrogen bonding through O–H group. Alcohols can act as both hydrogen bond donors (O–H) and acceptors (lone pair on O), forming strong intermolecular H-bonds. This requires extra energy to break → high bp. Ethers have no O–H, so they cannot form H-bonds with themselves (only accept H-bonds from other molecules). Example: ethanol (bp 78°C) vs dimethyl ether (bp −23°C), both C₂H₆O. Alcohols are also soluble in water due to H-bonding. Lower alcohols (up to C₄) are miscible with water in all proportions. Solubility decreases as alkyl chain length increases.
Q2
Lucas test distinguishes between primary, secondary, and tertiary alcohols. With Lucas reagent (conc. HCl + anhydrous ZnCl₂), which gives immediate turbidity (cloudiness) at room temperature?
Correct: C — Tertiary alcohol gives immediate turbidity. Lucas reagent = anhydrous ZnCl₂ + conc. HCl. The reaction is SN1 (ZnCl₂ coordinates to OH, making it a better leaving group, then carbocation forms). Tertiary alcohol → most stable tertiary carbocation → fastest reaction → immediate turbidity (insoluble alkyl chloride). Secondary alcohol → 5 min delay. Primary alcohol → no reaction at room temperature (no stable carbocation; requires heating). Methanol and ethanol do not react. This is a qualitative test to classify alcohols up to C₅ (higher alcohols are already insoluble).
Q3
The dehydration of alcohols with conc. H₂SO₄ follows which order of ease?
Correct: A — 3° > 2° > 1°. Dehydration of alcohols (E1 mechanism via carbocation): tertiary carbocations are most stable → formed most easily → 3° alcohols dehydrate at lowest temperature. Example: tert-butyl alcohol dehydrates at ~85°C; ethanol requires ~170°C. With conc. H₂SO₄ at 170°C, ethanol gives ethene; at 140°C it gives diethyl ether (intermolecular dehydration). For unsymmetrical alcohols, the major alkene product follows Zaitsev's rule (more substituted, more stable alkene is the major product).
Q4
Phenol is more acidic than ethanol (pKa ~10 vs ~16) because:
Correct: D — Resonance stabilisation of phenoxide ion. When phenol loses H⁺, the phenoxide anion C₆H₅O⁻ has its negative charge delocalised over the oxygen AND the ortho/para positions of the ring (5 resonance structures). This stabilises the anion, making it easier to form → phenol is more acidic. Ethoxide (C₂H₅O⁻) has no such delocalisation. Electron-withdrawing groups (–NO₂) on the ring increase acidity; electron-donating groups (–CH₃) decrease it. Phenol is more acidic than alcohols but less acidic than carboxylic acids (pKa ~5) and carbonic acid (pKa ~6.4).
Q5
Williamson synthesis is used to prepare:
Correct: B — Ethers via Williamson synthesis. Sodium alkoxide (R–O⁻Na⁺) + R'X → R–O–R' + NaX. Mechanism: SN2 (the alkoxide attacks the alkyl halide). Used to prepare both symmetrical and unsymmetrical ethers. For unsymmetrical ethers, the alkoxide should be derived from the more hindered alcohol, and the alkyl halide should be primary (to avoid elimination). Example: CH₃ONa + C₂H₅Cl → CH₃OC₂H₅ (methyl ethyl ether). Phenyl ethers (ArOR) can be made from sodium phenoxide + alkyl halide: C₆H₅ONa + RX → C₆H₅OR. This is an SN2 reaction, so 3° alkyl halides give mainly elimination products.
Q6
Oxidation of primary alcohols with mild oxidising agents (e.g., PCC — pyridinium chlorochromate) gives:
Correct: C — Aldehyde. Primary alcohol oxidation: (1) Mild oxidising agent (PCC, MnO₂) → stops at aldehyde stage; (2) Strong oxidising agent (K₂Cr₂O₇/H₂SO₄, KMnO₄) → goes to carboxylic acid. Secondary alcohol → ketone (with any oxidising agent; ketones resist further oxidation). Tertiary alcohol → no oxidation (no α-H on the OH carbon). Methanol oxidation: CH₃OH → HCHO (formaldehyde) → HCOOH (formic acid). Ethanol (breathalyser): CH₃CH₂OH → CH₃CHO → CH₃COOH (acetic acid). The Fehling's/Tollens' test distinguishes aldehydes (positive) from ketones (negative).
Q7
Which of the following reactions is characteristic of phenols but NOT of alcohols?
Correct: A — Phenol reacts with NaOH (a base) to form sodium phenoxide + water. Phenol is acidic enough (pKa ~10) to react with NaOH: C₆H₅OH + NaOH → C₆H₅ONa + H₂O. Alcohols (pKa ~16–18) do not react with NaOH. Both react with Na metal to liberate H₂. Phenol gives a distinctive violet/purple colour with neutral FeCl₃ (not alcohols). Phenol undergoes electrophilic aromatic substitution at o/p positions easily (–OH is strongly activating). Phenol reacts with Br₂ water to give 2,4,6-tribromophenol (white precipitate) — used as a test for phenol.
Q8
The reaction of phenol with Br₂ water gives:
Correct: D — 2,4,6-tribromophenol as white precipitate. The –OH group is a powerful activating and ortho/para-directing group in electrophilic aromatic substitution. With Br₂ water (aqueous bromine, no catalyst needed), all three available o/p positions are brominated instantly → 2,4,6-tribromophenol (white precipitate). This is used as a qualitative test for phenol. Contrast: bromination of benzene requires a Lewis acid catalyst (FeBr₃) and gives only monobromination. With CS₂ (non-polar solvent) at low temperature, bromination of phenol can be controlled to give mono products (ortho + para mixture).
Q9
Kolbe's reaction (Kolbe-Schmitt reaction) converts sodium phenoxide to:
Correct: B — Salicylic acid. Kolbe-Schmitt reaction: C₆H₅ONa + CO₂ (300°C, 5 atm) → sodium salicylate → acid workup → salicylic acid (2-hydroxybenzoic acid). Used industrially to make aspirin (acetylsalicylic acid = salicylic acid + acetic anhydride). Related reactions on phenol: Reimer-Tiemann reaction (CHCl₃ + NaOH) → salicylaldehyde (2-hydroxybenzaldehyde). Fries rearrangement: phenyl ester → (AlCl₃, heat) → o- and p-hydroxyacetophenone. Claisen rearrangement: allyl phenyl ether → (heat, no catalyst) → o-allylphenol.
Q10
Diethyl ether (C₂H₅OC₂H₅) has a much lower boiling point (35°C) than n-butanol (117°C) despite having the same molecular formula (C₄H₁₀O). This is because:
Correct: C — Ether lacks O–H for self-association through H-bonds. Both have formula C₄H₁₀O. Butanol has –OH group → forms strong intermolecular H-bonds (O–H···O), requiring much more energy to vaporise → bp 117°C. Ether has C–O–C (no O–H) → cannot donate H-bonds → only weak van der Waals forces → bp 35°C. Ethers can act as H-bond acceptors (lone pairs on O) but not donors. This is why ethers are good solvents for Grignard reactions (dissolve polar Mg compounds but don't react with them). Ether is also less dense than water and immiscible.
Q11
Reaction of ethanol with phosphorus trichloride (PCl₃) gives:
Correct: A — Chloroethane. Alcohols react with phosphorus halides to give alkyl halides: 3ROH + PCl₃ → 3RCl + H₃PO₃; ROH + PCl₅ → RCl + POCl₃ + HCl; ROH + SOCl₂ → RCl + SO₂ + HCl (best method — volatile SO₂ and HCl gas easily removed). The PCl₅ method gives inversion of configuration at a chiral centre (SN2-like). The SOCl₂ method can give retention or inversion depending on solvent. All three methods convert –OH to –Cl. Similarly, PBr₃ gives alkyl bromides. These are better than using HX for sensitive substrates.
Q12
Which of the following is NOT a correct statement about glycerol (propane-1,2,3-triol)?
Correct: D — The explosive made from glycerol is glyceryl trinitrate (nitroglycerin, GTN), NOT TNT. TNT (trinitrotoluene) is made from toluene, not glycerol. Glycerol + conc. HNO₃/H₂SO₄ → glyceryl trinitrate (nitroglycerin), an explosive used in dynamite (absorbed on kieselguhr by Alfred Nobel). Glycerol (HOCH₂CHOHCH₂OH) is a byproduct of saponification (fats + NaOH → soap + glycerol). It is hygroscopic, viscous, and sweet — used in cosmetics, food, and pharmaceuticals as a humectant. It has three –OH groups → extensive H-bonding → very high bp (290°C) and high viscosity.
Q13
The cleavage of ethers with HI gives:
Correct: B — Alkyl iodide + alcohol first; with excess HI, both become alkyl iodides. Ethers resist most chemical reactions (strong C–O bonds + no acidic H + no leaving group). Strong acid HI (or HBr) can cleave ethers: R–O–R' + HI → R–I + R'–OH (first cleavage); R'–OH + HI → R'–I + H₂O (second cleavage with excess HI). The C–O bond of the more substituted alkyl group breaks (SN2 or SN1 depending on substitution). HF is weakest acid and least effective. HI > HBr > HCl in reactivity for ether cleavage. Phenyl ethers (ArOR): only the alkyl–O bond cleaves (ArO–R), never the Ar–O bond.
Q14
Aspirin (acetylsalicylic acid) is prepared from salicylic acid by reaction with:
Correct: C — Acetic anhydride. Salicylic acid (2-hydroxybenzoic acid) + (CH₃CO)₂O → acetylsalicylic acid (aspirin) + CH₃COOH. The phenolic –OH is acetylated. Acetic anhydride is preferred over acetic acid (reaction is faster, goes to completion) and acetyl chloride (too reactive, may give side products). Aspirin is an analgesic, antipyretic, and anti-inflammatory drug (NSAID — inhibits cyclooxygenase enzyme, reducing prostaglandin synthesis). Methyl salicylate (oil of wintergreen) is the methyl ester of salicylic acid — used as a topical analgesic.
Q15
Ethanol is used as a fuel (flexible-fuel vehicles, E85 blend) because:
Correct: A — Renewable, high octane, clean burning. Ethanol (C₂H₅OH): high octane number (~109 research octane number) → anti-knock properties. Produced by fermentation of sugars (renewable). Burns more completely than petrol → fewer unburnt hydrocarbon emissions. Blended with petrol (E10, E85) to extend supply and reduce net CO₂ (plants absorb CO₂ during growth). Denatured alcohol (industrial spirit) = ethanol + small amounts of methanol or pyridine (to make it undrinkable, tax-free). Methanol is more toxic (causes blindness/death even in small amounts) — oxidised to formic acid in body which damages optic nerve.
Q16
The Victor Meyer test distinguishes primary, secondary, and tertiary alcohols. Which gives a red colour?
Correct: D — Primary → red, secondary → blue, tertiary → colourless. Victor Meyer test: alcohol → alkyl iodide (PI₃ or HI) → silver nitrite → nitroalkane → treat with HNO₂ → treat with KOH/NaOH: Primary alcohol → nitrous acid with –CH₂NO₂ → pseudo-nitrolic acid → red colour with KOH. Secondary → nitroso compound → blue colour. Tertiary → no α-H → no reaction with HNO₂ → colourless. This test is based on the reactivity of nitroalkanes with nitrous acid. Also useful: chromic acid test (Jones reagent) — primary and secondary alcohols give colour change (Cr⁶⁺ orange → Cr³⁺ green); tertiary alcohols give no colour change.
Q17
Phenol on treatment with excess conc. HNO₃/H₂SO₄ gives:
Correct: B — 2,4,6-trinitrophenol (picric acid). Phenol with dilute HNO₃ → mixture of 2-nitrophenol (major, steam-distillable, intramolecular H-bond) and 4-nitrophenol (minor, higher bp, intermolecular H-bond). With excess conc. HNO₃/H₂SO₄ → 2,4,6-trinitrophenol (picric acid, pale yellow crystals, mp 122°C). Picric acid is a strong acid (pKa 0.38), stronger than carboxylic acids, because three –NO₂ groups strongly stabilise the phenoxide anion. It is an explosive (used in Lyddite). Also used to form picrates (crystalline derivatives) for characterisation of organic compounds.
Q18
Fermentation of glucose gives ethanol and CO₂. The enzyme involved is:
Correct: C — Zymase. C₆H₁₂O₆ → (zymase, yeast, anaerobic) → 2C₂H₅OH + 2CO₂. Zymase is a mixture of enzymes present in yeast (Saccharomyces cerevisiae). Invertase converts sucrose → glucose + fructose. Amylase (diastase) converts starch → maltose. Maltase converts maltose → glucose. Maximum ethanol concentration achievable by fermentation is ~14–15% (higher concentrations kill the yeast). Industrial ethanol (absolute/anhydrous) is obtained by azeotropic distillation using benzene (removes water; forms benzene-water-ethanol ternary azeotrope which distils off, leaving anhydrous ethanol).
Q19
The order of acidity among the following is: phenol, water, ethanol, p-nitrophenol, p-cresol (p-methylphenol)
Correct: A — p-nitrophenol > phenol > p-cresol > water > ethanol. –NO₂ (electron-withdrawing by resonance and induction) at para position further stabilises phenoxide → more acidic. –CH₃ (electron-donating by hyperconjugation) destabilises phenoxide → less acidic than phenol. Water (pKa 15.7) is more acidic than ethanol (pKa 16–18) because the ethyl group pushes electrons onto oxygen (inductive effect), making O–H bond harder to break. Among phenols: EWG (–NO₂, –CN, –COOH, halogens) increase acidity; EDG (–CH₃, –OCH₃, –NH₂) decrease acidity.
Q20
Hydroboration-oxidation of propene (CH₃CH=CH₂) gives:
Correct: D — 1-propanol (anti-Markovnikov). Hydroboration-oxidation (H. C. Brown, Nobel 1979): BH₃ adds to alkene syn (cis) with B going to less substituted carbon (anti-Markovnikov, bulky BH₃ goes to less hindered end) → trialkylborane → H₂O₂/NaOH → alcohol with OH at less substituted carbon. Net result: syn addition of water across double bond, anti-Markovnikov regiochemistry. Contrast: acid-catalysed hydration (H₃O⁺) gives Markovnikov product (OH at more substituted carbon) = 2-propanol from propene. Hydroboration-oxidation gives 1-propanol from propene — useful for primary alcohol synthesis.
⚗️ Aldehydes, Ketones & Carboxylic Acids 8 marks
Score0 / 0
Q1
Tollens' reagent (ammoniacal silver nitrate) gives a silver mirror test positive with:
Correct: A — Aldehydes only. Tollens' reagent = [Ag(NH₃)₂]⁺ (silver diammine complex). Aldehydes (R–CHO) are reducing agents — they reduce Ag⁺ to Ag° (silver mirror on test tube walls): RCHO + 2[Ag(NH₃)₂]⁺ + 2OH⁻ → RCOO⁻ + 2Ag↓ + 4NH₃ + H₂O. Ketones (R–CO–R') do NOT reduce Tollens' reagent (no H on carbonyl C). Exception: formaldehyde (HCHO) reduces very strongly. Fehling's test (blue Cu²⁺ → red Cu₂O precipitate) also works with aldehydes but NOT aromatic aldehydes (C₆H₅CHO is not oxidised by Fehling's). Schiff's reagent turns pink/magenta with aldehydes.
Q2
Fehling's solution test is positive for:
Correct: C — Aliphatic aldehydes only. Fehling's solution = Fehling A (CuSO₄) + Fehling B (NaOH + sodium potassium tartrate). Aliphatic aldehydes reduce Cu²⁺ (blue) to Cu₂O (brick-red precipitate). Aromatic aldehydes (C₆H₅CHO) do NOT reduce Fehling's. Ketones do NOT reduce Fehling's. Tollens' reagent works for both aliphatic AND aromatic aldehydes. Schiff's reagent (decolourised rosaniline) gives pink/red with aldehydes — more sensitive than Tollens' or Fehling's. Benedict's solution is similar to Fehling's but more stable (used in urine glucose test).
Q3
Aldol condensation occurs between:
Correct: D — Carbonyl compounds with α-H + dilute base/acid. Aldol condensation: two molecules of acetaldehyde (CH₃CHO) + dil. NaOH → 3-hydroxybutanal (aldol = ald + ol: has both aldehyde and alcohol). On heating, aldol → α,β-unsaturated carbonyl compound (crotonaldehyde) by dehydration. Conditions: requires α-H (no α-H → Cannizzaro reaction); dilute NaOH (base) or dilute H⁺ (acid). Cross-aldol: two different carbonyl compounds → mixture of products (less useful synthetically unless one has no α-H). Acetone undergoes aldol: CH₃COCH₃ → diacetone alcohol (4-methyl-4-hydroxypent-2-one).
Q4
Cannizzaro reaction is undergone by:
Correct: B — Aldehydes with NO α-H + conc. NaOH. Cannizzaro reaction is a disproportionation: one aldehyde molecule is oxidised (→ carboxylate) while another is reduced (→ alcohol). Example: 2HCHO + NaOH → CH₃OH + HCOONa (formaldehyde → methanol + sodium formate). Benzaldehyde: 2C₆H₅CHO + NaOH → C₆H₅CH₂OH + C₆H₅COONa. Aldehydes with α-H prefer aldol condensation. Cross-Cannizzaro: HCHO + another aldehyde (no α-H) → HCOOH + other alcohol (HCHO is always the one oxidised — strongest reductant). Tilden's reaction: trichloroacetaldehyde (CCl₃CHO) undergoes Cannizzaro.
Q5
The nucleophilic addition of HCN to acetaldehyde (CH₃CHO) gives a product called:
Correct: A — Lactonitrile (cyanohydrin). CH₃CHO + HCN → CH₃CH(OH)CN (lactonitrile). Mechanism: CN⁻ (nucleophile) attacks the carbonyl carbon (electrophilic C in C=O) → tetrahedral alkoxide intermediate → protonation → cyanohydrin. Cyanohydrins can be hydrolysed to α-hydroxy acids: CH₃CH(OH)CN + H₂O/H⁺ → lactic acid (CH₃CH(OH)COOH). This is important: it is a method to increase the carbon chain by one carbon. Ketones also form cyanohydrins but reaction is slower (more hindered carbonyl). Acetone + HCN → acetone cyanohydrin → methacrylonitrile (basis of Perspex/Lucite synthesis).
Q6
Rosenmund reduction converts acyl chloride (RCOCl) to:
Correct: C — Aldehyde. Rosenmund reduction: RCOCl + H₂ → (Pd/BaSO₄, poisoned catalyst, xylene) → RCHO + HCl. The Pd catalyst is "poisoned" (partially deactivated with BaSO₄ or thiourea/quinoline) to prevent over-reduction to primary alcohol. Useful for preparing aromatic aldehydes from aromatic acyl chlorides. Other aldehyde preparations: (1) Stephen reaction: RCN + SnCl₂/HCl → imine → hydrolysis → RCHO (aliphatic and aromatic); (2) Etard reaction: ArCH₃ + CrO₂Cl₂ → ArCHO; (3) Gattermann-Koch: ArH + CO/HCl (AlCl₃, CuCl catalyst) → ArCHO (limited to benzene derivatives).
Q7
The carbonyl carbon in aldehydes and ketones is electrophilic because:
Correct: D — Oxygen is more electronegative (δ−), carbon is δ+. In C=O, oxygen (EN = 3.5) pulls the electron density toward itself: C^δ+–O^δ−. This makes the carbonyl carbon susceptible to nucleophilic attack (nucleophilic addition). After nucleophile adds to C, the C=O π bond breaks, oxygen gets the electron pair (forms alkoxide). In ketones, two alkyl groups donate electrons to carbonyl C (inductive effect) → less electrophilic than aldehydes. This is why aldehydes are more reactive towards nucleophilic addition than ketones. Formaldehyde is most reactive (no alkyl groups). Also steric: aldehydes have one H (less hindered) vs ketones (two R groups).
Q8
Hell-Volhard-Zelinsky (HVZ) reaction is used for:
Correct: B — α-halogenation of carboxylic acids. CH₃COOH + Br₂ (red P) → BrCH₂COOH (bromoacetic acid) + HBr. Mechanism: (1) P + Br₂ → PBr₃; (2) RCH₂COOH + PBr₃ → RCH₂COBr (acyl bromide, more reactive); (3) Br₂ adds at α-C to give α-bromo acyl bromide; (4) Hydrolysis → α-bromo acid. Red phosphorus acts as a catalyst. HVZ works only with carboxylic acids (not esters/ketones) because the acyl halide intermediate is key. The α-halo acid can be further converted to α-amino acid (by NH₃ displacement) or α-hydroxy acid (by NaOH hydrolysis).
Q9
Carboxylic acids have higher boiling points than alcohols of comparable molecular mass because:
Correct: A — Dimer formation through two H-bonds. Carboxylic acids exist as cyclic dimers (8-membered ring) in non-polar solvents and in the gas phase: two –COOH groups form two O–H···O hydrogen bonds simultaneously. This doubles the effective molecular mass → much higher bp. Example: acetic acid (CH₃COOH, MW 60, bp 118°C) vs ethanol (C₂H₅OH, MW 46, bp 78°C). The dimer of acetic acid has MW 120. Lower fatty acids (up to C₄) are liquids with pungent odour (rancid smell); butanoic acid (butyric acid) smells like rancid butter. Higher fatty acids (>C₁₀) are waxy solids.
Q10
The reaction of carboxylic acid with alcohol in the presence of conc. H₂SO₄ gives:
Correct: C — Ester (Fischer esterification). RCOOH + R'OH ⇌ RCOOR' + H₂O (conc. H₂SO₄ or dry HCl as catalyst, heat). Reversible reaction — equilibrium shifted right by removing water (azeotropic distillation, molecular sieves) or using excess alcohol. Mechanism: nucleophilic acyl substitution — alcohol O attacks the protonated carbonyl carbon. Acid derivatives in decreasing order of reactivity: acyl halide > anhydride > ester > amide > carboxylate. Hydrolysis of ester gives back acid + alcohol: RCOOR' + H₂O → RCOOH + R'OH (acid/base catalysis). Saponification (base hydrolysis of ester) is irreversible: RCOOR' + NaOH → RCOONa + R'OH.
Q11
Decarboxylation (loss of CO₂) of carboxylic acid occurs readily with:
Correct: D — Soda lime decarboxylation of carboxylate salts. RCOONa + NaOH (CaO) → R–H + Na₂CO₃. This is a dry distillation. Example: CH₃COONa + NaOH (soda lime) → CH₄ + Na₂CO₃. Useful in lab to prepare lower alkanes. Simple carboxylic acids do not decarboxylate easily on gentle heating (they require very high temperatures or special conditions). Exceptions that decarboxylate easily: β-keto acids (have carbonyl at β-position — cyclic 6-membered TS); malonic acid and oxalic acid on gentle heating. Kolbe's electrolysis: 2RCOONa + 2H₂O → R–R + 2CO₂ + H₂ (electrolysis; anode oxidation).
Q12
The reaction of CH₃MgBr (Grignard reagent) with CO₂ followed by hydrolysis gives:
Clemmensen reduction converts a carbonyl compound to:
Correct: A — C=O to CH₂ (Clemmensen reduction). Zn-Hg amalgam + conc. HCl → direct reduction of C=O to CH₂ (bypasses alcohol). Used in acidic conditions — suitable for acid-stable compounds. Example: PhCOCH₃ → PhCH₂CH₃. Wolff-Kishner reduction (NH₂NH₂ + KOH, ethylene glycol, 200°C) also achieves C=O → CH₂ but under basic conditions — suitable for base-stable (acid-labile) compounds. Meerwein-Ponndorf-Verley (MPV): C=O → CHOH using Al(OiPr)₃ (chemoselective — reduces C=O, not C=C). LiAlH₄ reduces C=O → CHOH (primary or secondary alcohol), RCOOH → RCH₂OH, RCOOR' → 2 alcohols. NaBH₄ reduces only C=O, not ester/acid (milder).
Q14
The acidity of carboxylic acids (pKa ~4–5) is much greater than that of alcohols (pKa ~16) because:
Correct: C — Resonance stabilisation of carboxylate anion. RCOO⁻ has two equivalent resonance structures with the negative charge equally distributed over both oxygens. Both C–O bonds in carboxylate are equivalent (intermediate between single and double bond, bond order = 1.5, length ~127 pm). This delocalisation greatly stabilises the anion → carboxylic acid readily donates H⁺. Alkoxide (RO⁻) has no such resonance. Electron-withdrawing groups (–Cl, –NO₂) near the COOH increase acidity (stabilise anion further by induction). Trichloroacetic acid (Cl₃CCOOH, pKa = 0.66) is far more acidic than acetic acid (pKa = 4.76).
Q15
Formaldehyde (HCHO) is unique among aldehydes because it:
Correct: D — Unique in many ways. Formaldehyde (HCHO): (1) Gas at RT (bp −21°C); formalin = 40% aq. solution (preservative). (2) No α-H → undergoes Cannizzaro reaction (2HCHO + NaOH → CH₃OH + HCOONa). (3) Most reactive carbonyl compound (no steric/electronic hindrance). (4) Reduces Tollens' (very strong reducing agent — actually reduces ammoniacal silver so well that it's used for silvering mirrors). (5) Does not show tautomerism (no α-H). (6) Forms polyoxymethylene (paraformaldehyde) on standing. (7) Reacts with ammonia to give hexamethylenetetramine (urotropine, C₆H₁₂N₄) — antiseptic. (8) Carcinogen at high concentrations.
Q16
Which compound gives a positive iodoform test AND a positive Tollens' test?
Correct: B — Acetaldehyde (CH₃CHO). Acetaldehyde has: CH₃CO– group → positive iodoform test (gives CHI₃); R–CHO (aldehyde group) → positive Tollens' test (silver mirror). Acetone: positive iodoform (CH₃CO– present), but negative Tollens' (ketone — no H on carbonyl C). Benzaldehyde: positive Tollens' (aldehyde), but negative iodoform (C₆H₅CO– group — phenyl, not methyl attached to C=O). Propanal (C₂H₅CHO): positive Tollens', but negative iodoform (no CH₃CO– group, has C₂H₅CO–). So only acetaldehyde satisfies both conditions simultaneously.
Q17
The Beckmann rearrangement converts a ketoxime to:
Correct: C — Amide. Beckmann rearrangement: ketoxime (R₂C=NOH) + H₂SO₄ (or PCl₅) → amide (RCONHR'). For cyclohexanone oxime → ε-caprolactam (cyclic amide) + H₂SO₄ → lactam (industrially used to make Nylon-6 polymer). Mechanism: OH of oxime is protonated → leaves as water → the group anti (trans) to OH migrates to nitrogen with its electrons → nitrilium ion → water adds → amide. The group that migrates is the one trans to OH (stereospecific). This is used in industrial synthesis of polyamides. Named after Ernst Otto Beckmann (1886).
Q18
Which of the following is the most acidic?
Correct: A — Trichloroacetic acid (pKa = 0.66), strongest of these. Three Cl atoms are strong electron-withdrawing groups (–I effect via induction). They withdraw electron density from the carboxylate anion, stabilising the negative charge → easier to donate H⁺ → more acidic. pKa values: CCl₃COOH (0.66) < CHCl₂COOH (1.48) < CH₂ClCOOH (2.86) < CH₃COOH (4.76) < (CH₃)₃CCOOH (5.05). Electron-donating alkyl groups destabilise carboxylate anion → less acidic. Benzoic acid (pKa 4.20) is slightly more acidic than acetic acid due to inductive withdrawal by the ring (not resonance donation at COOH position).
Q19
The reaction of acetic acid with PCl₅ gives:
Correct: D — Acetyl chloride (acyl chloride) + POCl₃ + HCl. CH₃COOH + PCl₅ → CH₃COCl + POCl₃ + HCl. Also: 3CH₃COOH + PCl₃ → 3CH₃COCl + H₃PO₃; CH₃COOH + SOCl₂ → CH₃COCl + SO₂ + HCl. Acyl chlorides are the most reactive acid derivatives (good for making other derivatives). Reactivity order of acid derivatives toward nucleophilic acyl substitution: RCOCl > (RCO)₂O > RCOOR' > RCONH₂. Acyl chlorides hydrolyse vigorously with water, react with alcohol (→ ester), with NH₃ (→ amide), with RNH₂ (→ N-substituted amide), with RCOO⁻ Na⁺ (→ anhydride). Example: CH₃COCl + NH₃ → CH₃CONH₂ + HCl.
Q20
The Gattermann-Koch reaction is used to prepare:
Correct: B — Aromatic aldehydes (ArCHO) via Gattermann-Koch. ArH + CO + HCl → (AlCl₃, CuCl, high pressure) → ArCHO. Effective for benzene and its derivatives. Cannot be used for phenols/phenol ethers (deactivated by Lewis acid). Gattermann reaction (modified): ArH + HCN/HCl → (AlCl₃) → ArCH=NH (imine) → hydrolysis → ArCHO (works for phenols too). Kolbe-Schmitt: sodium phenoxide + CO₂ → sodium salicylate → salicylaldehyde (Reimer-Tiemann reaction uses CHCl₃/NaOH). Friedel-Crafts acylation (RCOCl/AlCl₃) gives ketone ArCOR, not aldehyde (since formyl chloride HCOCl is unstable). Hence Gattermann-Koch is the standard method for ArCHO.
🔬 Amines 6 marks
Score0 / 0
Q1
The correct decreasing order of basic strength of methylamine (CH₃NH₂), aniline (C₆H₅NH₂), and ammonia (NH₃) in aqueous solution is:
Correct: C — CH₃NH₂ > NH₃ > Aniline. Basicity: the availability of the lone pair on N determines base strength. CH₃NH₂: methyl group donates electrons (inductive effect) → lone pair more available → stronger base than NH₃. Aniline (C₆H₅NH₂): lone pair on N delocalised into the aromatic ring (resonance) → lone pair less available → weakest base. pKb values (lower = stronger base): CH₃NH₂ (3.38) < NH₃ (4.74) < Aniline (9.38). In gas phase: CH₃NH₂ > (CH₃)₂NH > (CH₃)₃N > NH₃. In aqueous solution: (CH₃)₂NH > CH₃NH₂ > (CH₃)₃N > NH₃ (solvation effect modifies order for tertiary amine).
Q2
Hofmann bromamide degradation converts an amide (RCONH₂) to:
Correct: A — Primary amine with one fewer C. RCONH₂ + Br₂ + NaOH → RNH₂ + CO₂ + NaBr + H₂O. Mechanism: amide → N-bromo amide → rearrangement (Lossen-type: N migrates to carbonyl C) → isocyanate (R–N=C=O) → hydrolysis → RNH₂ + CO₂. Key: the carbonyl C is lost as CO₂ → product amine has one C fewer. Example: CH₃CH₂CONH₂ (propanamide) → CH₃CH₂NH₂ (ethylamine). This is an important method to prepare primary amines (compare with Gabriel synthesis which also gives 1° amines). Also: reduction of nitro compounds → primary amines; reduction of nitriles → primary amines (LiAlH₄).
Q3
Diazotisation of primary aromatic amine (aniline) with NaNO₂/HCl at 0–5°C gives:
Correct: D — Benzene diazonium chloride. C₆H₅NH₂ + NaNO₂ + HCl (0–5°C) → C₆H₅N₂⁺Cl⁻ + NaCl + H₂O. Diazonium salts are formed only below 5°C (unstable at higher temperatures). Above 5°C: diazonium hydrolyses → phenol + N₂. Diazonium salts are key intermediates in aromatic synthesis: Sandmeyer → ArCl, ArBr, ArCN; Balz-Schiemann → ArF; with H₃PO₂ → ArH (deamination); with aq. NaOH → ArOH; coupling with phenol/amine → azo dye (Ar–N=N–Ar'). Azo coupling: C₆H₅N₂⁺ + C₆H₅OH → p-hydroxyazobenzene (orange dye). Azo dyes are used as textile dyes, pH indicators.
Q4
The Hinsberg test distinguishes 1°, 2°, and 3° amines. Benzenesulfonyl chloride (C₆H₅SO₂Cl) reacts with secondary amine to give:
Correct: B — N,N-disubstituted sulfonamide, insoluble in NaOH. Hinsberg test results: Primary amine (RNH₂) + C₆H₅SO₂Cl → N-monosubstituted sulfonamide (R–NH–SO₂C₆H₅) → has acidic N–H → dissolves in NaOH → forms N-sulfonamide sodium salt. Secondary amine (R₂NH) + C₆H₅SO₂Cl → N,N-disubstituted sulfonamide (R₂N–SO₂C₆H₅) → NO acidic N–H → insoluble in NaOH (precipitate). Tertiary amine (R₃N) → does NOT react with C₆H₅SO₂Cl (no N–H) → no sulfonamide → amine dissolves in HCl (amine + HCl → ammonium salt, water-soluble) but not in Hinsberg reagent directly.
Q5
Primary aliphatic amine reacts with HNO₂ (NaNO₂ + HCl) at room temperature to give:
Correct: A — Unstable aliphatic diazonium salt decomposes at RT. 1° aliphatic amine + HNO₂ → aliphatic diazonium ion (R–N₂⁺) — highly unstable, decomposes immediately at room temperature (unlike aromatic diazonium) → N₂ gas + carbocation → products: alcohol (+ H₂O), alkene (+ H⁺), alkyl chloride (+ Cl⁻). Useful as: N₂ gas evolution confirms 1° aliphatic amine. Contrast: 1° aromatic amine → stable diazonium salt at 0–5°C (aromaticity stabilises). 2° amine + HNO₂ → N-nitrosamine (R₂N–NO, yellow oily liquid, possible carcinogen). 3° aliphatic amine + HNO₂ → forms salt (R₃N·HNO₂) — no N–NO formation since no N–H.
Q6
Aniline (C₆H₅NH₂) is less basic than aliphatic amines because:
Correct: C — Lone pair delocalisation into ring. In aniline, the N lone pair overlaps with the π system of the ring (conjugation). This is evidenced by: (1) N is nearly sp² hybridised (not sp³); (2) C–N bond length in aniline (140 pm) is shorter than in alkylamines (147 pm) — partial double bond character; (3) Aniline is planar or nearly planar. This delocalisation reduces electron density on N → weak base (Kb much smaller than alkylamines). Consequence: aniline is far less nucleophilic than alkylamines → requires more vigorous conditions for N-alkylation. pKb: aniline = 9.38; NH₃ = 4.74; methylamine = 3.38.
Q7
Reduction of nitrobenzene with Fe/HCl (or Sn/HCl) gives:
Correct: D — Aniline. C₆H₅NO₂ + 6[H] → (Fe/HCl or Sn/HCl, acidic) → C₆H₅NH₂ + 2H₂O. Industrial preparation: catalytic hydrogenation of nitrobenzene (Fe catalyst, 300°C) or chemical reduction. Partial reduction intermediates: NO₂ → NO → NHOH → NH₂. With Zn/NH₄Cl (neutral medium) → C₆H₅NHOH (phenylhydroxylamine). With Zn/NaOH → azoxybenzene (C₆H₅N(O)=NC₆H₅). With LiAlH₄ → aniline. Aniline is the starting material for many synthetic dyes (mauveine — first synthetic dye by W.H. Perkin 1856), pharmaceuticals (sulfa drugs), rubber chemicals, and polyurethanes.
Q8
Coupling reaction of diazonium salt with aniline gives:
Correct: B — Azo compound (orange/yellow dye). Diazonium coupling: C₆H₅N₂⁺Cl⁻ + C₆H₅NH₂ (slightly alkaline/neutral) → C₆H₅–N=N–C₆H₄–NH₂ (p-aminoazobenzene, an orange dye). The electrophilic diazonium cation (weak electrophile) attacks the activated ring (phenol or aromatic amine) at the para position (preferentially). At pH < 5 (acid): couples with aniline to give diazoamino compound (ArN=N–NHAr). At pH 5–9 (slightly alkaline): couples at p-position of aniline → azo compound. With phenol: in alkaline medium (phenoxide form is more reactive) → orange azo dye. Orange II, Congo Red, methyl orange are important azo dyes/indicators.
Q9
Bromination of aniline with Br₂ water gives:
Correct: A — 2,4,6-tribromoaniline. The –NH₂ group is strongly activating (ortho/para director) → all three o/p positions brominated rapidly by Br₂ water (no catalyst needed). Similar to phenol + Br₂ water. To get monobromo product, the –NH₂ group must be deactivated: acetylation of aniline (CH₃CO)₂O → acetanilide (–NHCOCH₃), then brominate (–NHCOCH₃ is still activating but less so) → 4-bromoacetanilide → hydrolysis → 4-bromoaniline. This is the Acetylation-bromination-hydrolysis sequence for preparing para-substituted aniline derivatives. Acetylation also protects the amine from strong oxidising conditions.
Q10
Which amine gives a red-orange precipitate with carbylamine test (CHCl₃ + alc. KOH)?
Correct: C — Primary amines only. Carbylamine test (isocyanide test): 1° amine + CHCl₃ + alc. KOH → isocyanide (R–N≡C, carbylamines) with extremely offensive smell. Mechanism: CHCl₃ + KOH → :CCl₂ (dichlorocarbene) → reacts with R–NH₂ → R–N=CCl₂ → KOH removes 2HCl → R–N≡C (isocyanide). Both aliphatic and aromatic 1° amines give this test. 2° and 3° amines → no reaction (no N–H for initial step). This test is specific for 1° amines. Isocyanides are poisonous. Mnemonic: Primary → Positive isocyanide; Secondary and Tertiary → No carbylamine.
Q11
Methyl orange is a commonly used acid-base indicator that is:
Correct: D — Methyl orange is an azo dye. Methyl orange = p-(dimethylaminoazobenzene)sulfonic acid sodium salt. Structure: (CH₃)₂N–C₆H₄–N=N–C₆H₄–SO₃Na. pH range: 3.1 (red) to 4.4 (yellow/orange). Prepared by: diazotisation of sulphanilic acid → coupling with dimethylaniline. In acidic form: –N=N– protonated → quinonoid structure (red). In basic form: azo form (yellow). Methyl orange is used as an indicator in strong acid–strong base and strong acid–weak base titrations (pH change is in acidic range). Examples of azo dyes: Congo Red (pH 3–5, blue-violet to red), Orange II, malachite green (triphenylmethane dye, not azo).
Q12
N,N-dimethylaniline reacts with benzene diazonium chloride. The product is:
Correct: B — p-dimethylaminoazobenzene. C₆H₅N₂⁺ + C₆H₅N(CH₃)₂ → p-CH₃)₂N–C₆H₄–N=N–C₆H₅ (para coupling). N,N-dimethylaniline has no N–H, so coupling occurs on the ring at the para position (N is still activating: lone pair conjugated into ring makes p-position highly electron-rich). This dye was once used as a food colourant ("butter yellow") but is now banned (carcinogen). The azo linkage (–N=N–) is the chromophore responsible for colour. Extended conjugation (aromatic rings connected by –N=N–) absorbs visible light. Auxochromic groups (–OH, –NH₂, –N(CH₃)₂) modify colour/intensity. Bathochromic shift: absorption moves to longer wavelength (red shift).
Q13
Acetylation of aniline with acetic anhydride gives:
Correct: A — Acetanilide. C₆H₅NH₂ + (CH₃CO)₂O → C₆H₅NHCOCH₃ (acetanilide) + CH₃COOH. This is nucleophilic acyl substitution — the amine N attacks the carbonyl C of acetic anhydride. Acetanilide was the first synthetic pharmaceutical drug (analgesic/antipyretic, introduced 1886 as "Antifebrin"). Acetylation of aniline is used in organic synthesis to: (1) Protect the –NH₂ group from oxidation; (2) Reduce its activating power for selective halogenation at para position; (3) The acetamido group (–NHCOCH₃) is still ortho/para directing but less activating than –NH₂. After the desired reaction, hydrolysis removes the acetyl group to regenerate the amine.
Q14
The correct order of boiling points for methylamine (CH₃NH₂), dimethylamine ((CH₃)₂NH), and trimethylamine ((CH₃)₃N) is:
Correct: C — (CH₃)₂NH (7°C) > CH₃NH₂ (−6°C) > (CH₃)₃N (3°C). Boiling points of amines depend on: (1) H-bonding capacity (N–H bonds) — 1° and 2° amines form H-bonds (N–H···N); 3° amines cannot (no N–H). (2) Molecular mass. CH₃NH₂: 1°, 2 N–H, bp −6°C. (CH₃)₂NH: 2°, 1 N–H, but higher MW → bp 7°C. (CH₃)₃N: 3°, no N–H → only van der Waals → despite higher MW, bp is 3°C (lower than (CH₃)₂NH). So trimethylamine has surprisingly low bp due to lack of H-bonding. N–H···N H-bonds are weaker than O–H···O (N is less electronegative than O), so amines have lower bp than corresponding alcohols.
Q15
Sulpha drugs (sulfonamides) like sulfanilamide work by:
Correct: D — Competitive inhibitor of PABA. Sulfonamides are structurally similar to para-aminobenzoic acid (PABA, H₂N–C₆H₄–COOH), which bacteria use to synthesise folic acid (needed for nucleotide synthesis). Sulfonamides competitively inhibit the enzyme that uses PABA → bacteria cannot make folic acid → cannot grow/divide. Humans get folic acid from diet (no de novo synthesis) → sulfonamides selectively toxic to bacteria. Sulfanilamide (para-aminobenzenesulfonamide): H₂N–C₆H₄–SO₂NH₂. First sulfa drug (Prontosil, 1932, Gerhard Domagk, Nobel Prize 1939). Later replaced largely by penicillin antibiotics. Used in urinary tract infections and some other bacterial infections still.
🧬 Biomolecules 4 marks
Score0 / 0
Q1
Glucose (C₆H₁₂O₆) on reaction with Tollens' reagent gives a silver mirror. This indicates that glucose:
Correct: B — Free aldehyde group; glucose is a reducing sugar. Glucose (aldohexose) has a free –CHO group in its open-chain form. This reduces Tollens' (Ag⁺ → Ag) and Fehling's (Cu²⁺ → Cu₂O). All monosaccharides are reducing sugars. Among disaccharides: maltose (1α→4 glycosidic bond, free reducing end) and lactose are reducing; sucrose (1α→2β linkage between both anomeric carbons) is non-reducing. Reducing sugars reduce Benedict's/Fehling's/Tollens'. This is the basis of Benedict's test for blood glucose. Glucose is also known as dextrose (D-glucose, dextrorotatory). D-glucose: all –OH groups in R configuration except C2 (in D-fructose, C2 has different config).
Q2
The open-chain structure of glucose shows it is an aldohexose. In aqueous solution, glucose predominantly exists as:
Correct: C — Glucopyranose (6-membered ring), ~99% in solution. Glucose C1 –CHO reacts intramolecularly with C5 –OH to form a hemiacetal (ring): this creates a new chiral centre at C1 (anomeric carbon). α-D-glucopyranose: –OH at C1 is axial (on the same side as the ring oxygen in Haworth); β-D-glucopyranose: –OH at C1 is equatorial (trans to C6 –CH₂OH in Haworth). Mutarotation: α-D-glucose ([α]D = +112.2°) ↔ open chain ↔ β-D-glucose ([α]D = +18.7°), equilibrium at +52.5°. β-D-glucose is more stable (all equatorial groups in chair conformation). Fructose forms furanose (5-membered) ring more commonly.
Q3
Sucrose is a non-reducing sugar because:
Correct: A — Both anomeric carbons engaged in glycosidic bond. Sucrose = α-D-glucopyranose + β-D-fructofuranose linked by α(1→2)β glycosidic bond between C1 of glucose (anomeric) and C2 of fructose (anomeric). Both reducing ends are blocked → no free –CHO or hemiketal → cannot open chain → non-reducing. Hydrolysis of sucrose (invertase enzyme or dilute HCl) → glucose + fructose (this mixture is called invert sugar; optical rotation inverts from +66.5° for sucrose to −19.9° for the mixture because fructose, −92.3°, is more strongly levorotatory). Table sugar is sucrose (C₁₂H₂₂O₁₁). Lactose: glucose + galactose, C1 of galactose linked to C4 of glucose (galactose C1 is free → reducing).
Q4
The difference between starch and cellulose lies in:
Correct: D — α vs β glycosidic linkage is the key difference. Starch = amylose (unbranched, α-1,4 links, helical) + amylopectin (branched, α-1,4 main chain + α-1,6 at branch points, every 24–30 glucose units). Human enzyme (amylase, amyloglucosidase) can cleave α(1→4) and α(1→6) bonds. Cellulose: β(1→4) links → linear, hydrogen-bonded chains → fibrous, insoluble, structural role in plant cell walls. Humans lack cellulase enzyme → cannot digest cellulose (dietary fibre). Glycogen: like amylopectin but more branched (α-1,6 branch every 8–10 units) — animal storage polysaccharide. Iodine test: starch gives blue-black (amylose helix traps I₂ molecules); glycogen gives brownish-red; cellulose gives no colour.
Q5
The peptide bond in proteins is formed between:
Correct: B — –COOH + –NH₂ → –CO–NH– + H₂O (condensation). The peptide bond (amide bond): –CO–NH– is formed by condensation (loss of water) between the carboxyl group of one amino acid and the amino group of the next. Dipeptide has 1 peptide bond; tripeptide has 2; protein has n−1 peptide bonds for n amino acids. The peptide bond has partial double bond character (resonance: –C(=O)–NH– ↔ –C(–O⁻)=NH–) → planar, slightly rigid (~6 atoms coplanar). Protein backbone forms regular structures: α-helix (secondary structure, intrachain H-bonds between C=O and N–H four residues apart); β-sheet (interchain H-bonds, pleated sheet). R groups determine the tertiary structure.
Q6
Denaturation of a protein means:
Correct: C — Loss of 3D structure, not primary structure. Denaturation disrupts non-covalent interactions (H-bonds, hydrophobic interactions, van der Waals, ionic bonds) and some covalent interactions (disulfide bonds with reducing agents) that maintain secondary, tertiary, quaternary structure. Causes: heat, extreme pH, urea, organic solvents, heavy metal ions. The primary structure (sequence of amino acids, peptide bonds) is NOT destroyed. Protein loses biological activity because active site shape is disrupted. Often irreversible (e.g., boiling an egg — egg white albumin denatures). Renaturation (refolding) is possible in some cases (e.g., RNase experiment by Anfinsen — denatured with urea, renatured by removing urea, regained activity; proved primary structure determines protein folding).
Q7
An essential amino acid is one that:
Correct: A — Must be obtained from diet (cannot be synthesised in body). There are 20 standard amino acids in proteins. Essential amino acids (8–9 for adults): valine, leucine, isoleucine, phenylalanine, tryptophan, methionine, threonine, lysine (and histidine for children/infants). Non-essential: can be synthesised by the body (e.g., glycine, alanine, aspartate, glutamate). All amino acids (except proline) are α-amino acids with the structure: H₂N–CH(R)–COOH. At physiological pH (7.4), amino acids exist as zwitterions: ⁺H₃N–CH(R)–COO⁻. Isoelectric point (pI): pH at which zwitterion form predominates (net charge = 0); electrophoresis — at pI, amino acid/protein does not migrate.
Q8
The complementary base pairing in DNA (Watson-Crick model) is:
Correct: D — A=T (2 H-bonds) and G≡C (3 H-bonds). Watson-Crick double helix (1953): two antiparallel strands held together by H-bonds between complementary bases: Adenine–Thymine: 2 hydrogen bonds; Guanine–Cytosine: 3 hydrogen bonds. G≡C pairs are stronger → DNA with higher G+C content has higher melting temperature (Tm). Chargaff's rules: [A] = [T] and [G] = [C] in double-stranded DNA (derived from this pairing). In RNA, Thymine is replaced by Uracil (U) — RNA has A–U base pairs (also 2 H-bonds). The helix makes one full turn every 10 base pairs (3.4 nm pitch, 0.34 nm per base pair, 2 nm diameter). The two strands are antiparallel: one is 5'→3', other is 3'→5'.
Q9
The nucleotide is composed of:
Correct: B — Base + sugar + phosphate. Nucleoside = nitrogenous base + pentose sugar (no phosphate). Nucleotide = nucleoside + phosphate group. DNA: deoxyribose (2'-deoxyribose) + bases A/G/C/T + phosphate. RNA: ribose + bases A/G/C/U + phosphate. Purine bases: Adenine (A) and Guanine (G) — two-ring (bicyclic). Pyrimidine bases: Cytosine (C), Thymine (T), Uracil (U) — one ring. Sugar is attached to base via N-glycosidic bond. Phosphodiester bond links 3'-OH of one nucleotide to 5'-phosphate of the next (backbone of nucleic acid). ATP (adenosine triphosphate) = nucleotide with 3 phosphates — energy currency of the cell.
Q10
The difference between DNA and RNA is that:
Correct: C — DNA: deoxyribose + T; RNA: ribose + U. Key differences: (1) Sugar: DNA = 2'-deoxyribose (no –OH at C2'); RNA = ribose (–OH at C2'). (2) Base: DNA has Thymine (T, 5-methyluracil); RNA has Uracil (U). Both have A, G, C. (3) Strands: DNA = typically double-stranded helix; RNA = typically single-stranded (but can form secondary structures). (4) Location: DNA mainly in nucleus + mitochondria; RNA in nucleus + cytoplasm + ribosome. Types of RNA: mRNA (messenger, carries genetic code from DNA to ribosome); tRNA (transfer, brings amino acids); rRNA (ribosomal, structural/catalytic in ribosome). (5) Function: DNA = storage of genetic information; RNA = expression of genetic information.
Q11
Enzymes are biological catalysts. They are:
Correct: A — Mostly proteins; some ribozymes (RNA). Enzymes are biological catalysts that: (1) Lower activation energy (Ea) of reactions. (2) Are highly specific (lock-and-key model: Emil Fischer; induced-fit model: Koshland). (3) Not consumed in reactions. (4) Work at mild conditions (body temperature, physiological pH). (5) Can be regulated (allosteric, competitive/non-competitive inhibition). The active site is a specific pocket/groove where substrate binds. Coenzymes (non-protein organic cofactors, often vitamins like NAD⁺/NADH derived from Niacin/B₃) assist enzymes. Metalloenzymes have metal ions (Zn²⁺ in carbonic anhydrase, Fe in haemoglobin, Mg²⁺ in chlorophyll). Ribozymes: RNA with catalytic activity (e.g., ribonuclease P, ribosomal peptidyl transferase activity).
Q12
Vitamins are classified as fat-soluble and water-soluble. Which group contains fat-soluble vitamins?
Correct: D — Vitamins A, D, E, K are fat-soluble (stored in fatty tissues/liver). Fat-soluble (ADEK): A (retinol, vision, night blindness if deficient); D (calciferol, calcium/bone metabolism, rickets if deficient); E (tocopherol, antioxidant); K (phylloquinone, blood clotting, synthesised by gut bacteria). Water-soluble: Vitamin C (ascorbic acid, collagen synthesis, scurvy if deficient) and all B vitamins (B₁ thiamine, B₂ riboflavin, B₃ niacin/nicotinamide, B₅ pantothenic acid, B₆ pyridoxine, B₇ biotin, B₉ folic acid, B₁₂ cobalamin). Water-soluble vitamins are not stored → must be consumed regularly. Fat-soluble can accumulate → toxicity possible with over-supplementation (hypervitaminosis A, D).
Q13
Which statement about fructose is correct?
Correct: B — Fructose is a ketohexose (keto at C2), sweetest natural sugar. Fructose (C₆H₁₂O₆) = levulose = fruit sugar. Keto group at C2, 4 –OH groups, –CH₂OH at C6. Despite having no aldehyde, fructose gives a positive Tollens' and Fehling's test because in basic conditions, fructose (ketose) undergoes tautomerism (enolisation) to form glucose and mannose (aldoses) via 1,2-enediol intermediate, and the aldose reduces the reagent. Fructose is levorotatory ([α]D = −92.3°). Relative sweetness: Fructose (1.73) > sucrose (1.0) > glucose (0.74) > maltose (0.32) > lactose (0.16). In the ring form, fructose exists primarily as furanose (5-membered ring: C2 keto + C5 –OH).
Q14
Lipids (fats and oils) are esters of:
Correct: C — Glycerol (propane-1,2,3-triol) + 3 fatty acids = triglyceride. Fats: triglycerides where fatty acids are saturated (no C=C double bonds) — solid at RT (e.g., butter, lard). Oils: unsaturated fatty acids (one or more C=C double bonds) — liquid at RT (e.g., olive oil, sunflower oil). Unsaturated fats → lower melting point (cis double bonds prevent close packing). Hydrogenation of oils (Ni catalyst) → margarine (saturated fat). Saponification: fat + NaOH → soap (sodium salt of fatty acid) + glycerol. Soap works by forming micelles (hydrophobic tail → oil, hydrophilic head → water). Phospholipids: glycerol + 2 fatty acids + phosphate + organic group → cell membrane bilayer. Waxes: long-chain alcohol + long-chain fatty acid ester (not glycerol-based).
Q15
Primary structure of a protein refers to:
Correct: A — Primary structure = amino acid sequence. Levels of protein structure: (1) Primary: sequence of amino acids linked by peptide bonds — determined by DNA sequence. (2) Secondary: local regular structures — α-helix (right-handed coil, intrachain H-bonds between C=O of residue n and N–H of residue n+4); β-sheet (extended, interchain H-bonds, parallel or antiparallel). (3) Tertiary: overall 3D shape of single polypeptide — maintained by H-bonds, disulfide bridges (–S–S–, Cys residues), hydrophobic interactions, salt bridges. (4) Quaternary: arrangement of multiple polypeptide subunits (e.g., haemoglobin has 2α + 2β subunits). Insulin: first protein to have primary structure determined (Sanger, 1955, Nobel Prize). Myoglobin: first 3D structure solved (Kendrew, 1958, Nobel 1962).
Q16
Lactose (milk sugar) is a disaccharide made of:
Correct: D — Galactose–glucose with β(1→4) bond; reducing sugar. Lactose = β-D-galactopyranose + D-glucopyranose linked by β(1→4) glycosidic bond. The C1 of glucose is free → reducing sugar (gives positive Tollens' and Fehling's). Hydrolysed by enzyme lactase (β-galactosidase) in the small intestine; lactose intolerance = deficiency of lactase. Maltose = glucose + glucose (α-1,4 bond) — reducing sugar (one free C1 anomeric OH); formed from starch hydrolysis (amylase). Sucrose = glucose + fructose (α-1,2β bond) — non-reducing (both anomeric carbons blocked). Cellobiose = glucose + glucose (β-1,4) — from cellulose hydrolysis; reducing sugar.
Q17
The iodine test for starch gives a blue-black colour because:
Correct: B — I₂ trapped in amylose helix (charge-transfer complex). Amylose (unbranched component of starch, α-1,4 linkages) adopts a helical coil structure. I₂ molecules fit snugly inside the helix, forming a charge-transfer complex (starch-iodine) that absorbs light at ~620 nm → blue-black colour. On heating, helix unwinds → I₂ released → colour disappears; on cooling → colour returns. Amylopectin (branched, α-1,4 and α-1,6) gives reddish-brown colour (shorter helical segments). Glycogen (most branched) gives brownish-red to no colour. This is a very sensitive test for starch; used in titrations as an indicator (starch-I₂ endpoint turns blue-black). Vitamin C (ascorbic acid) decolourises iodine (used in iodometric assay).
Q18
Haemoglobin is an example of a protein with:
Correct: C — Quaternary structure: 2α + 2β subunits + haem groups. Haemoglobin (Hb): MW ~64,000; four subunits (2α-chains + 2β-chains). Each subunit contains one haem group (iron-porphyrin complex with Fe²⁺ at centre). Fe²⁺ binds O₂ reversibly → carries O₂ in blood. Cooperative binding: binding of O₂ to one subunit increases affinity of other subunits (sigmoidal O₂ binding curve). CO binds haem ~240× more strongly than O₂ → CO poisoning. Myoglobin: single polypeptide (tertiary structure) with one haem → O₂ storage in muscles. Sickle cell anaemia: single amino acid mutation (Glu6→Val in β-chain) → HbS forms fibres when deoxygenated → sickle-shaped RBCs. Insulin: primary structure was first determined (Sanger); two chains (A and B) linked by disulfide bridges.
Q19
Which of the following is a nucleoside (not a nucleotide)?
Correct: A — Adenosine (base + sugar, no phosphate) is a nucleoside. Nucleoside = nitrogenous base + pentose sugar. Nucleotide = nucleoside + phosphate group(s). Nucleosides: adenosine (A + ribose), guanosine (G + ribose), cytidine (C + ribose), uridine (U + ribose), thymidine (T + deoxyribose). Deoxynucleosides have deoxyribose (d-prefix). Nucleotides: AMP, ADP, ATP (1, 2, 3 phosphates). ATP hydrolysis → ADP + Pᵢ releases ~30 kJ/mol (energy currency). cAMP (cyclic AMP): formed from ATP by adenylyl cyclase → second messenger in hormonal signalling. Drugs targeting nucleoside/nucleotide metabolism: zidovudine (AZT, HIV treatment — nucleoside reverse transcriptase inhibitor).
Q20
Glycogen is described as the "animal starch" because:
Correct: D — More branched than starch (amylopectin), α-1,4 + α-1,6 bonds. Glycogen: polysaccharide of glucose with α-1,4 main chain and α-1,6 branch points every 8–10 residues (vs amylopectin's every 24–30). More branching → more ends available for rapid glucose release (during exercise, stress) by glycogen phosphorylase. Stored in liver (regulates blood glucose) and muscle (local energy for contraction). Starvation → glycogen depleted in ~24h. Glycogen storage diseases (e.g., Pompe, McArdle) result from enzyme defects. Gives reddish-brown colour with iodine (not blue-black like starch, because shorter helical segments). Molecular weight of glycogen can be very large (10⁷–10⁸ Da). Insulin promotes glycogen synthesis (glycogenesis); glucagon promotes glycogen breakdown (glycogenolysis).