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ChemistryClass 123 markshard

Coordination Compounds

Explain the splitting of d orbitals in an octahedral crystal field according to crystal field theory.

Reveal model answer + marking points

According to crystal field theory, the bonding between the metal and the ligands is purely electrostatic. In an isolated metal ion the five d orbitals have the same energy (degenerate). When six ligands approach along the axes in an octahedral field, they repel the d orbitals unequally: the two orbitals pointing along the axes (dx2-y2 and dz2, called eg) are repelled more and rise in energy, while the three orbitals pointing between the axes (dxy, dyz, dzx, called t2g) are repelled less and are lowered in energy. This energy gap between t2g and eg is the crystal field splitting energy (delta o).

Marking-scheme points

  • Metal-ligand bonding treated as electrostatic
  • Six ligands approach along the axes (octahedral)
  • d orbitals split into lower t2g and higher eg; gap = delta o
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ChemistryClass 123 marksmedium

Haloalkanes and Haloarenes

How are haloalkanes prepared from alcohols? Write the reactions.

Reveal model answer + marking points

Haloalkanes are commonly prepared from alcohols by replacing the -OH group with a halogen. (1) With hydrogen halides: R-OH + HX -> R-X + H2O (reactivity of alcohols is 3 degrees > 2 degrees > 1 degree). (2) With phosphorus halides: 3R-OH + PCl3 -> 3R-Cl + H3PO3, and R-OH + PCl5 -> R-Cl + POCl3 + HCl. (3) With thionyl chloride (the best method, as the by-products are gases): R-OH + SOCl2 -> R-Cl + SO2 + HCl.

R-OH + SOCl2 -> R-Cl + SO2 + HCl

Marking-scheme points

  • R-OH + HX -> R-X + H2O
  • 3R-OH + PCl3 -> 3R-Cl + H3PO3
  • R-OH + SOCl2 -> R-Cl + SO2 + HCl (best method)
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ChemistryClass 123 markshard

Haloalkanes and Haloarenes

Distinguish between the SN1 and SN2 mechanisms of nucleophilic substitution.

Reveal model answer + marking points

In the SN2 (substitution nucleophilic bimolecular) mechanism, the reaction occurs in a single step; the nucleophile attacks the carbon from the side opposite the leaving group, and bond breaking and bond making occur simultaneously. Its rate depends on both the substrate and the nucleophile, and it gives inversion of configuration (Walden inversion); it is favoured by primary halides. In the SN1 (substitution nucleophilic unimolecular) mechanism, the reaction occurs in two steps through a carbocation intermediate; its rate depends only on the substrate, and it usually gives a racemic mixture. It is favoured by tertiary halides and polar protic solvents.

Marking-scheme points

  • SN2: one step, backside attack, inversion; rate depends on both reactants; favoured by primary halides
  • SN1: two steps via carbocation; rate depends only on substrate; racemisation
  • SN1 favoured by tertiary halides and polar protic solvents
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ChemistryClass 123 marksmedium

Alcohols, Phenols and Ethers

How are alcohols prepared by the hydration of alkenes and by the reduction of aldehydes and ketones?

Reveal model answer + marking points

(1) Acid-catalysed hydration of alkenes: an alkene adds water in the presence of dilute sulphuric acid following Markovnikov's rule to give an alcohol, e.g. CH2=CH2 + H2O -> CH3CH2OH. (2) Reduction of carbonyl compounds: aldehydes on reduction (with H2/Ni or NaBH4 or LiAlH4) give primary alcohols (R-CHO -> R-CH2OH), and ketones on reduction give secondary alcohols (R-CO-R' -> R-CH(OH)-R'). Alcohols can also be prepared from Grignard reagents reacting with carbonyl compounds.

R-CHO + 2[H] -> R-CH2OH

Marking-scheme points

  • Hydration of alkenes (Markovnikov): CH2=CH2 + H2O -> CH3CH2OH
  • Reduction of aldehyde -> primary alcohol
  • Reduction of ketone -> secondary alcohol
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ChemistryClass 123 marksmedium

Aldehydes, Ketones and Carboxylic Acids

Why do aldehydes and ketones undergo nucleophilic addition reactions? Give one example.

Reveal model answer + marking points

The carbonyl group (C=O) is polar because oxygen is more electronegative than carbon, so the carbon carries a partial positive charge and the oxygen a partial negative charge. This makes the carbonyl carbon electrophilic, so it is readily attacked by nucleophiles, leading to nucleophilic addition. For example, with hydrogen cyanide (HCN), the addition gives a cyanohydrin: R-CHO + HCN -> R-CH(OH)-CN. Aldehydes are more reactive than ketones towards nucleophilic addition due to less steric hindrance and a greater positive charge on the carbonyl carbon.

R-CHO + HCN -> R-CH(OH)-CN

Marking-scheme points

  • C=O is polar; carbonyl carbon is electrophilic (partial positive)
  • Nucleophile attacks the carbonyl carbon (nucleophilic addition)
  • Example: R-CHO + HCN -> R-CH(OH)-CN (cyanohydrin)
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ChemistryClass 123 marksmedium

Aldehydes, Ketones and Carboxylic Acids

Why are carboxylic acids more acidic than phenols? How do electron-withdrawing groups affect their acidity?

Reveal model answer + marking points

Carboxylic acids are more acidic than phenols because the carboxylate ion formed after the loss of the proton is stabilised by resonance in which the negative charge is spread equally over two electronegative oxygen atoms, making it very stable. In the phenoxide ion the negative charge is mainly on one oxygen and partly on less electronegative ring carbons, so it is less stabilised. Electron-withdrawing groups (like -Cl or -NO2) increase acidity because they further disperse and stabilise the negative charge of the carboxylate ion (for example, chloroacetic acid is stronger than acetic acid), while electron-releasing groups decrease acidity.

Marking-scheme points

  • Carboxylate ion: charge spread equally over two oxygen atoms (very stable)
  • Phenoxide ion is less stabilised
  • Electron-withdrawing groups increase acidity; electron-releasing groups decrease it
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ChemistryClass 123 marksmedium

Amines

How are primary amines prepared by the reduction of nitro compounds and by Hofmann's bromamide reaction?

Reveal model answer + marking points

(1) Reduction of nitro compounds: a nitro compound is reduced (with H2/Ni, or Sn/HCl, or Fe/HCl) to a primary amine; for example, nitrobenzene is reduced to aniline, C6H5NO2 + 6[H] -> C6H5NH2 + 2H2O. (2) Hofmann's bromamide degradation: an amide is treated with bromine and a strong alkali (Br2 + NaOH/KOH) to give a primary amine with one carbon atom less than the amide, R-CONH2 + Br2 + 4NaOH -> R-NH2 + Na2CO3 + 2NaBr + 2H2O.

R-CONH2 + Br2 + 4NaOH -> R-NH2 + Na2CO3 + 2NaBr + 2H2O

Marking-scheme points

  • Reduction of nitro compound -> primary amine (nitrobenzene -> aniline)
  • Hofmann bromamide: amide + Br2 + NaOH -> amine with one carbon less
  • R-CONH2 + Br2 + 4NaOH -> R-NH2 + Na2CO3 + 2NaBr + 2H2O
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ChemistryClass 123 marksmedium

Amines

Why are amines basic in nature? Compare the basic strength of amines in the gaseous phase.

Reveal model answer + marking points

Amines are basic because the nitrogen atom has a lone pair of electrons which it can donate to a proton (or to a Lewis acid), forming a bond; thus amines can accept a proton. In the gaseous phase (or a non-aqueous medium), only the inductive effect of the alkyl groups operates: more alkyl groups increase the electron density on nitrogen, so the basic strength follows the order tertiary > secondary > primary > ammonia. In aqueous solution the order changes because of the combined effect of inductive effect, solvation (hydrogen bonding of the cation) and steric hindrance.

Marking-scheme points

  • Amines are basic: nitrogen lone pair accepts a proton
  • Gas phase (inductive effect only): tertiary > secondary > primary > ammonia
  • Aqueous order differs due to solvation and steric effects
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ChemistryClass 123 marksmedium

Amines

How is benzenediazonium chloride prepared? Write one of its reactions (Sandmeyer reaction).

Reveal model answer + marking points

Benzenediazonium chloride is prepared by diazotisation: aniline is treated with nitrous acid (formed from sodium nitrite and hydrochloric acid) at a low temperature of 0 to 5 degrees C, C6H5NH2 + NaNO2 + 2HCl -> C6H5N2Cl + NaCl + 2H2O. In the Sandmeyer reaction, the diazonium group is replaced by a halogen or cyanide using the corresponding copper(I) salt; for example, C6H5N2Cl + CuCl -> C6H5Cl + N2. Diazonium salts are very useful for introducing many groups into the benzene ring.

C6H5NH2 + NaNO2 + 2HCl -> C6H5N2Cl + NaCl + 2H2O

Marking-scheme points

  • Diazotisation: aniline + NaNO2 + HCl at 0-5 degrees C -> C6H5N2Cl
  • Sandmeyer reaction: replace N2+ with Cl/Br/CN using Cu(I) salts
  • C6H5N2Cl + CuCl -> C6H5Cl + N2
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ChemistryClass 123 marksmedium

Biomolecules

What are proteins? What is meant by denaturation of a protein?

Reveal model answer + marking points

Proteins are naturally occurring biomolecules that are polymers of alpha-amino acids joined by peptide bonds (-CO-NH-); they are essential for growth and maintenance of the body and act as enzymes, hormones and structural materials. Denaturation of a protein is the process in which a protein loses its natural three-dimensional shape (its secondary and tertiary structure) due to heat, change in pH, or addition of chemicals, while the primary structure (sequence of amino acids) remains intact. On denaturation the protein loses its biological activity; for example, the coagulation of egg white on boiling.

Marking-scheme points

  • Proteins are polymers of alpha-amino acids linked by peptide bonds
  • Denaturation: loss of secondary and tertiary structure (shape)
  • Caused by heat/pH/chemicals; loses biological activity (e.g. boiling egg white)
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MathsClass 123 marksmedium

Relations and Functions

Show that the relation R on the set of integers Z defined by aRb if (a - b) is divisible by 3 is an equivalence relation.

Reveal model answer + marking points

Reflexive: for any integer a, a - a = 0, which is divisible by 3, so (a, a) in R. Symmetric: if (a - b) is divisible by 3, then (b - a) = -(a - b) is also divisible by 3, so aRb implies bRa. Transitive: if (a - b) and (b - c) are both divisible by 3, then their sum (a - b) + (b - c) = (a - c) is also divisible by 3, so aRb and bRc imply aRc. Since R is reflexive, symmetric and transitive, it is an equivalence relation.

Marking-scheme points

  • Reflexive: a - a = 0 divisible by 3
  • Symmetric: (a - b) divisible => (b - a) divisible
  • Transitive: sum (a - b) + (b - c) = (a - c) divisible; hence equivalence
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MathsClass 123 marksmedium

Relations and Functions

Show that the function f: R -> R given by f(x) = 2x + 3 is a bijection.

Reveal model answer + marking points

One-one: suppose f(x1) = f(x2). Then 2x1 + 3 = 2x2 + 3, so 2x1 = 2x2 and x1 = x2; hence f is one-one. Onto: let y be any real number in the codomain. Solving y = 2x + 3 gives x = (y - 3)/2, which is a real number, and f((y - 3)/2) = y. So every y has a pre-image, and f is onto. Being both one-one and onto, f is a bijection.

Marking-scheme points

  • One-one: f(x1) = f(x2) leads to x1 = x2
  • Onto: for any y, x = (y - 3)/2 is a valid pre-image
  • Both hold, so f is a bijection
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MathsClass 123 marksmedium

Relations and Functions

If f: R -> R is given by f(x) = 2x + 3, find its inverse function.

Reveal model answer + marking points

Since f is a bijection, its inverse exists. Let y = f(x) = 2x + 3. Solve for x in terms of y: y - 3 = 2x, so x = (y - 3)/2. Therefore the inverse function is f inverse (y) = (y - 3)/2, or writing in terms of x, f inverse (x) = (x - 3)/2. We can check that f(f inverse (x)) = x.

f inverse (x) = (x - 3)/2

Marking-scheme points

  • Put y = 2x + 3 and solve for x
  • x = (y - 3)/2
  • f inverse (x) = (x - 3)/2
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MathsClass 123 markshard

Inverse Trigonometric Functions

Prove that tan inverse (1) + tan inverse (2) + tan inverse (3) = pi.

Reveal model answer + marking points

First combine tan inverse (2) + tan inverse (3). Using tan inverse (x) + tan inverse (y) = pi + tan inverse ((x + y)/(1 - xy)) when xy > 1: here x = 2, y = 3, xy = 6 > 1, so tan inverse (2) + tan inverse (3) = pi + tan inverse ((5)/(1 - 6)) = pi + tan inverse (-1) = pi - pi/4 = 3pi/4. Adding tan inverse (1) = pi/4: total = pi/4 + 3pi/4 = pi. Hence proved.

tan inverse x + tan inverse y = tan inverse((x + y)/(1 - xy))

Marking-scheme points

  • Use tan inverse x + tan inverse y = pi + tan inverse((x+y)/(1-xy)) when xy > 1
  • tan inverse 2 + tan inverse 3 = 3pi/4
  • Add tan inverse 1 = pi/4 to get pi
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MathsClass 123 marksmedium

Matrices

If A = [[1, 2],[3, 4]] and B = [[2, 0],[1, 3]], find the product AB.

Reveal model answer + marking points

To multiply, each element of a row of A is multiplied by the corresponding element of a column of B and summed. AB = [[(1)(2) + (2)(1), (1)(0) + (2)(3)], [(3)(2) + (4)(1), (3)(0) + (4)(3)]] = [[2 + 2, 0 + 6], [6 + 4, 0 + 12]] = [[4, 6], [10, 12]].

(AB)ij = sum of (row i of A)(column j of B)

Marking-scheme points

  • Multiply rows of A by columns of B and add
  • AB = [[2+2, 0+6],[6+4, 0+12]]
  • AB = [[4, 6],[10, 12]]
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MathsClass 123 marksmedium

Matrices

Show that any square matrix A can be written as the sum of a symmetric and a skew-symmetric matrix.

Reveal model answer + marking points

Write A = (1/2)(A + A') + (1/2)(A - A'). Let P = (1/2)(A + A') and Q = (1/2)(A - A'). Then P' = (1/2)(A + A')' = (1/2)(A' + A) = P, so P is symmetric. And Q' = (1/2)(A - A')' = (1/2)(A' - A) = -(1/2)(A - A') = -Q, so Q is skew-symmetric. Since A = P + Q, every square matrix is the sum of a symmetric matrix P and a skew-symmetric matrix Q.

A = (1/2)(A + A') + (1/2)(A - A')

Marking-scheme points

  • Take P = (1/2)(A + A') and Q = (1/2)(A - A')
  • P' = P (symmetric); Q' = -Q (skew-symmetric)
  • A = P + Q
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MathsClass 123 marksmedium

Determinants

Using determinants, find the area of the triangle whose vertices are (1, 0), (6, 0) and (4, 3).

Reveal model answer + marking points

The area of a triangle with vertices (x1, y1), (x2, y2), (x3, y3) is (1/2)|x1(y2 - y3) + x2(y3 - y1) + x3(y1 - y2)|. Substituting: area = (1/2)|1(0 - 3) + 6(3 - 0) + 4(0 - 0)| = (1/2)|-3 + 18 + 0| = (1/2)(15) = 7.5 square units.

Area = (1/2)|x1(y2-y3) + x2(y3-y1) + x3(y1-y2)|

Marking-scheme points

  • Area = (1/2)|x1(y2-y3) + x2(y3-y1) + x3(y1-y2)|
  • = (1/2)|-3 + 18 + 0|
  • = 7.5 square units
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MathsClass 123 marksmedium

Determinants

Find the inverse of the matrix A = [[2, 3],[1, 4]] using the adjoint method.

Reveal model answer + marking points

First find the determinant: |A| = (2)(4) - (3)(1) = 8 - 3 = 5, which is non-zero, so the inverse exists. For a 2 x 2 matrix [[a, b],[c, d]], the adjoint is [[d, -b],[-c, a]], so adj A = [[4, -3],[-1, 2]]. Then the inverse is A inverse = (1/|A|) adj A = (1/5)[[4, -3],[-1, 2]] = [[4/5, -3/5],[-1/5, 2/5]].

A inverse = (1/|A|) adj A

Marking-scheme points

  • |A| = 8 - 3 = 5 (non-zero, so inverse exists)
  • adj A = [[4, -3],[-1, 2]]
  • A inverse = (1/5)[[4, -3],[-1, 2]]
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MathsClass 123 markshard

Determinants

Solve the system of equations 2x + 3y = 8 and x + 2y = 5 using determinants (Cramer's rule).

Reveal model answer + marking points

Write D = determinant of coefficients = |[[2, 3],[1, 2]]| = (2)(2) - (3)(1) = 4 - 3 = 1. Dx (replace first column by constants) = |[[8, 3],[5, 2]]| = (8)(2) - (3)(5) = 16 - 15 = 1. Dy (replace second column by constants) = |[[2, 8],[1, 5]]| = (2)(5) - (8)(1) = 10 - 8 = 2. By Cramer's rule, x = Dx/D = 1/1 = 1 and y = Dy/D = 2/1 = 2. So x = 1, y = 2.

x = Dx/D, y = Dy/D

Marking-scheme points

  • D = 1, Dx = 1, Dy = 2
  • Cramer's rule: x = Dx/D, y = Dy/D
  • x = 1, y = 2
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MathsClass 123 marksmedium

Continuity and Differentiability

Find the value of k for which the function f(x) = kx + 1 for x <= 5 and f(x) = 3x - 5 for x > 5 is continuous at x = 5.

Reveal model answer + marking points

For continuity at x = 5, the left-hand limit, the right-hand limit and f(5) must all be equal. Left-hand value (using kx + 1): f(5) = 5k + 1. Right-hand limit (using 3x - 5): as x approaches 5, 3(5) - 5 = 10. For continuity, 5k + 1 = 10, so 5k = 9, giving k = 9/5.

LHL = RHL = f(a)

Marking-scheme points

  • Left value at 5: 5k + 1; right limit at 5: 3(5) - 5 = 10
  • Equate for continuity: 5k + 1 = 10
  • k = 9/5
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