Notes for XII (ISC): prepared by S.Narayana Iyer, M.Sc, M.

Phil

MODEL ANSWERS TO SPECIMEN QUESTION PAPER FOR XII ISC BOARD EXAMINATION 2012 CHEMISTRY Paper – 1 (THEORY) (Three Hours) (Candidates are allowed additional 15 minutes for only reading the paper. They must NOT start writing during this time) -----------------------------------------------------------------------------------------------------Answer all questions in Part I and six questions from Part II, choosing two questions from Section A, two from Section B and two from Section C. All working, including rough work, should be done on the same sheet as, and adjacent to, the rest of the answer. The intended marks for questions or parts of questions are given in brackets [ ]. Balanced equations must be given wherever possible and diagrams where they are helpful. When solving numerical problems, all essential working must be shown. In working out problems use the following data: Gas Constant R = 1.987 cal deg-1 mol-1 = 8.314 JK-1 mol-1 = 0.0821 dm3 atm K-1mol-1 1 l atm = 1 dm3 atm = 101.3 J. 1 Faraday = 96500 Coulombs. -----------------------------------------------------------------------------------------------------------PART I (Answer all questions) Question 1 (a) Fill in the blanks by choosing the appropriate word/words from those given in brackets: [5] (electron, proton, neutron, decreases, increasing, lowering, one, two, acidic, basic, anion, cation, paramagnetic, Lewis acid, Lewis base, carbonic acid, sulphurous acid, sulphuric acid, ammonium carbonate, sodium bicarbonate, six, increases) (i) A positive catalyst _______ the rate of a reaction by _____ the activation energy. (ii) Human blood is a buffer solution of _________ and _________. (iii) BF3 is a _________ since it is an _________ deficient molecule. (iv) Oxygen is ________ due to the presence of ______ unpaired electrons. (v) A solution of FeCl3 is ________ due to ________ hydrolysis. ANSWER (i) increases, lowering (ii) carbonic acid, sodium bicarbonate (iii) Lewis acid, electron (iv) paramagnetic, two (v) acidic, cation (b) Complete the following statements by selecting the correct alternative from the choices given: [5] (i) [Co(NH3)5Br] SO4 and [Co(NH3)5SO4] Br exhibit 1. Coordination isomerism. 2. Ionisation isomerism. 1

(v) How is the free energy change related to the enthalpy and entropy change of a substance? ANSWER (i) ΔTf for NaCl = 0. For normal molecules like glucose ΔTf will not be doubled. 0. (iii) Out of the following solutions.01 M Na2SO4 . 0. the one having the highest boiling point will be: 1.0123oC NaCl(s) + aq = Na+(aq) + Cl-(aq) 1 mol 1mol 1mol In solution the number of particles is doubled. (ii) Cannizzaros’ reaction is given by: 1.01 M KNO3 . Acetone.0123 o = 0. What will be the depression of freezing point caused by a 1 M glucose solution? (ii) What happens to the pH of a solution containing equimolar amount of acetic acid and sodium acetate when a few drops of dilute HCl is added? Give reason. Ethanol. Hydrate isomerism.01 M Urea. 2.3. (iv) The bond angle of water is: 1. 90o 2. 3. 3. What is the unit of molar conductivity? (iv) Give the electrode reactions of the galvanic cell in which the reaction Zn(s) + 2 Ag+ (aq) → Zn+2(aq) + 2 Ag(s) takes place. four 2.01 M Glucose. eight ANSWER (i) ionization isomerism (ii) Formaldehyde (iii) 0. Geometrical isomerism.3 4. 107. 0. Reason: A solution containing equimolecular amount of acetic acid and sodium acetate is Buffer solution which has a constant pH value and which is not affected by adding a small amount of another acid or 2 . 120o (v) The co-ordination number of each ion in copper crystals is: 1. 4. 4.01M Na2SO4 (iv) 105o (v) twelve (c) Answer the following questions: [5] o (i) The depression of freezing point caused by a 1M NaCl solution is 0. (iii) Express the relationship between molar conductivity and specific conductivity of a solution.00615 C 2 (ii) There is no change in the pH value of the solution. 4. fourteen 4. 0. So ΔTf for glucose = 0.0123 C. 105o o 3. Acetaldehyde. Formaldehyde 2. twelve 3. So the colligative properties are also doubled.

base (iii) k x 1000 Molarity Λm = molar conductivity k = specfic conductivity Unit of molar conductivity = ohm-1 cm2 mol-1 Λm = (iv) At anode Zn(s) → Zn2+ + 2eAt cathode 2Ag+(aq) + 2e. two from Section B and two from Section C. SECTION A (Answer any two questions) Question 2 3 .→ 2Ag(s) (v) Δ G = Δ H .TΔ S ΔG = Free energy change at constant T and P ΔH = Enthalpy change ΔS = Entropy change T = Absolute temperature [5] (d) Match the following: (i) Buffer solution (a) Co-ordinate bond (ii) Co-ordination compounds (b) Raoult’s Law (iii) Dilute solution (c) Warner’s Theory (iv) Ammonium ion (d) Faraday’s Law (v) Electrolysis (e) Henderson’s equation ANSWER (i) Buffer solution (e) Henderson’s equation (ii) Co-ordination compounds (c) Warner’s Theory (iii) Dilute solution (b) Raoult’s Law (iv) Ammonium ion (a) Co-ordinate bond (v) Electrolysis (d) Faraday’s Law PART II Answer six questions choosing two from Section A.

p wM = o p Wm m is the molecular mass of the solid substace (solute) m= m= wM ⎛ po ⎞ ⎜ ⎟ W ⎝ po − p ⎠ 2. the vapour pressure of the solution is 600 mm Hg.6 39 ⎝ ⎠ (ii) Calculate the standard enthalpy change for a reaction CO2(g) + H2(g) → CO(g) + H2O(g).5. What is the molecular mass of the solid substance? [3] ANSWER The vapour pressure of pure solvent benzene (po) = 640 mm Hg The vapour pressure of solution (p) = 600 mm Hg Mass of solid substance (solute) (w) = 2.0 g of benzene. CO(g) and H2O(g) are – 393.8) . and – 248 KJ mol-1 respectively.5 + (-244.175 g is added to 39.ions.2 kJmol-1 (b) Give reasons for the following: (i) A solution of copper sulphate is acidic in nature. – 110. Given that ΔHfo for CO2(g).It dissociates almost completely in aqueous solution into Cu2+ and SO42.5. [3] ANSWER ΔHoreaction = ∑ ΔHfo(products) . When a non-volatile and non-electrolyte solid weighing 2.(a) (i) The vapour pressure of pure benzene at a certain temperature is 640 mm Hg.(-393. 4 . [2] ANSWER Copper sulphate is a salt of strong acid H2SO4 and a weak base Cu(OH)2.5) = -355.5 = 38.175g Mass of solvent (W) = 39g Molecular mass of solvent benzene (C6H6) (M) = 78 For a very dilute solution po .∑ ΔHfo(reactants) ΔHoreaction = -110.3 + 393.175 x 78 ⎛ 640 ⎞ ⎜ 640 − 600 ⎟ = 69.

ions the undissociated water molecules dissociate to keep the value of Kw constant.C. Their molecular weight remains the same and hence boiling point does not increase too much. unit cell of an edge 200 pm.023 x 1023 = 50. Hence the solution becomes acidic.Assication of molecules does not take place.19 24 x 1023 4 x 50.66 g/cm3 ρ= -10 3 23 ( 200 x 10 ) x 6.19 = 41. [1] 5 .C.nitrophenol. [2] Ortho nitrophenol possesses intramolecular hydrogen bonding. Calculate its density if 200g of this element contains 24 x 1023 atoms. This increases the H+ ion concentration in solution.CuSO4 Cu2+ + SO42Cu2+ ions being conjugate of a weak base Cu(OH)2 act as a strong acid and take up OHions furnished by water to form weakly dissociated Cu(OH)2.023 x 10 Zm a3 N o (ii) Draw the electron dot structure of perchloric acid clearly distinguishing between the electrons of each atom. Question 3 (a) (i) An element crystallizes in a structure having F. (ii) The boiling point of p-nitrophenol is more than that of o . Their molecular weight increases and hence boiling point increases. [3] ANSWER ρ= M= 200 x 6. 2H2O 2H+ + 2OHCu2+ + 2OHCu(OH)2 In order to compensate the decrease of OH. Paranitrophenol possesses intermolecular hydrogen bonding. Association of molecules takes place.

0 x 10-2 0.6 x 10-3 0.0 x 10-2 Calculate: 6 .2 1.E Ea = activation energy Et = Threshold energy E = average kinetic energy actually possessed by the molecules Or Activation energy is the difference between the energy of activated complex and that of the reactants. of A (mol l-1) Conc. of B (mol l-1) Initial rate (mol l-1 S-1) 0. [3] Conc.1 1. (ii) Consider the following data for the reaction A + B → Products. Ea = Et .1 4. So the activation energy Ea can be calculated.5 0.5 1.5 0.303 R.2 0. k = Ae-Ea/RT k = rate constant A = a constant which is proportional to the frequency of collisions between reactant molecules R = molar gas constant T = temperature in Kelvin When a graph is plotted between log k and 1/T a straight line is obtained.0 x 10-4 0. The slope of the line is equal to –Ea/2.1 0.Perchloric acid (HClO4) (b) (i) What is the activation energy of a reaction? How is the rate constant of a reaction related to the activation energy? How can activation energy be calculated from this relationship? [3] ANSWER The excess amount of energy which the reactants must attain so that their collisions bring about actual chemical reaction is called activation energy.

1] q ---------------------equation 3 1.2 order with respect to A is 2 p q Dividing equation 3 by equation 4 k ⎡ 0.2] p [0.04 L/mol/s [A]2 0.5 ⎤ ⎡ 0.0 x 10-2 = k [0. ANSWER (i) Suppose the order with respect to A is p and with respect to B is q.5 ⎠ k ⎡ 0.equation 4 Dividing equation 1 by equation 3 p k ⎡ 0.0 x 10−4 ⎛ 0.1] q ---------------------equation 1 1.5] q--------------------.2] q ---------------------equation 2 1.1⎤ ⎡ 0.04 = [0.1 x 102 Question 4 (a) (i) What is the type of hybridization in PCl5 molecule? Explain why PCl5 is very 7 .0 x 10−4 = = 0.0 x 10−2 k ⎡ 0.5] p [0.1⎤ 1.1⎤ ⎣ ⎦ ⎣ ⎦ 0. Then the rate law is: rate = k [A]p [B]q Substituting the values from experiment 4.1] p [0.2 log 1 q= =0 log 0.5⎤ ⎣ ⎦ ⎣ ⎦ ⎛ 0.5⎤ ⎡ 0.6 x 10-3 = k [0.5] p [0.1⎤ 4.2 log 0.(1) The order with respect to A and B for the reaction.0 x 10-2 = k [0.0 x 10-4 = k [0.0 x 10−2 ⎝ 0.0 x 10−2 = ⎣ ⎦p ⎣ ⎦q 1.2 order with respect to B = 0 Total order with respect to A and B = 2 + 0 = 2 (ii) rate = k [A]2 [B]0 k= rate 4.5 ⎠ q p q log 1 = q log 0.04 p= =2 log 0.1 ⎞ ⎣ ⎦ ⎣ ⎦ = ⎟ p q = ⎜ 1.2]p log 0. (2) The rate constant of the reaction.1 ⎞ 1= ⎜ ⎟ ⎝ 0.5⎤ ⎡ 0.04 = p log 0.

3979) = 2. of 0.reactive in nature. (ii) When H2S is passed through a solution of acidified copper nitrate and zinc nitrate.1 M CH3COOH is mixed with 200 ml of 0.8 x 10-5 + log10 10 H H 0.745 + ( −2. only copper is precipitated as sulphide 8 . ANSWER Sp3d hybridization ( Trigonal bipyramidal hybridization ) The five hybrid orbitals are not equivalent.3471 b) Give reasons why: [5] (i) Aluminium trichloride exists as a dimmer.5 x 1000 [ ] 200 [0. what will be the pH of the resulting mixture? [3] ANSWER Henderson's equation Ka [salt] H p = p + log10 [salt] Ka p for acetic acid = 1.8 x 10-5 + log10 10 H p = .log 1.8 x 10-5 p = .5] [ p = 4. (ii) If 100 ml.5 M CH3COONa.1x100 ] 1000 0.01] [2.log 1. [2] Since PCl5 has not a regular structure as it has two bond angles 90o and other three bond angles 120o it is highly reactive.

The solubility product of sulphide of zinc is very high (cations of group IV) When hydrogen sulphide is passed through zinc nitrate solution in acid medium only CuS gets precipitated. Thus both aluminium atoms in the dimer achieve octets.ANSWER (i) In AlCl3 aluminium atom has only 6 electrons in its outermost shell. The sulphide ion concentration is not enough to exceed the very high Ksp of ZnS. In acid medium the dissociation of H2S is suppressed due to common ion effect.to achieve stability the molecule exists as dimer. . So it is not precipitated. ANSWER (ii) The solubility product of sulphide of copper is very low. The apparatus consists of an electrically heated copper vessel which acts as the cathode.(cations of group II). [3] In Whytlaw Gray’s method fluorine is prepared by the electrolysis of fused KHF2.During the formation of dimmer one chlorine atom of one molecule donates a lone pair of electrons to the aluminium atom of the other molecule resulting in the formation of two dative bonds. H2S HCl 2H+ + S2H+ + Cl- (acid) So the sulphide ion concentration is low. The graphite rod is enclosed in a copper diaphragm perforated at the bottom.→ H2 9 . This is enough to exceed the very low Ksp of CuS.A pure graphite rod is used as anode. The diaphragm prevents the mixing of hydrogen liberated at the cathode and fluorine liberated at the anode. So it gets precipitated. SECTION B (Answer any two questions) Question 5 (a) Explain how fluorine is prepared by the electrolysis of potassium hydrogen fluoride. To achieve octet ie. KHF2 → KF + HF HF → H+ + FAt cathode: 2H+ + 2e.

C. Question 6 (a) Name the following compounds according to I. (c) Draw the geometrical isomers of the compound [Co (NH3)2 Cl2] [1] ANSWER 10 . [2] ANSWER (i) 2F2 + 2NaOH → 2NaF + H2O + OF2 (oxygen difluoride) (ii) K2O + H2O → 2KOH 2KOH + 5O3 → 2KO3 + 5O2 + H2O KO3 is potassium ozonide. So it does not give the usual tests for Fe2+ ion.A.At anode: 2F.2e.ion.U.P. It is orange coloured solid and contains the paramagnetic O3. K4 [Fe (CN) 6] H2 O 4K+ + Fe [(CN) 6]4- Ferrocyanide ion is a complex ion and does not ionize into constituent ions. rules: (i) [Co(NH3)6] Cl3 (ii) K[Pt Cl3(NH3)] [2] ANSWER (i) Hexaamminecobalt (III)chloride (ii) Potassiumamminetrichloroplatinate(II) (b) Explain why an aqueous solution of potassium hexcyanoferrate(II) does not give a test for ferrous ion. [1] ANSWER Potassium hexacyanoferrate(II) K4 [Fe (CN) 6] is a co-ordination compound and contains the complex ion Fe [(CN) 6]4and the co-ordination compound dissociates into K+ ion and Fe [(CN) 6]4. (b) Give balanced equations for each of the following reactions: (i) Fluorine and dilute NaOH..ion when dissolved in water.→ F2 Fluorine is liberated at anode and is stored in steel cylinders. (ii) Ozone and aqueous potassium oxide.

10H2O) crystallizes out. Sodium dichromate Na2Cr2O7. [1] K3[Fe(C2O4)3] Question 7 (a) Write the steps involved in the preparation of potassium dichromate from chromite ore. STEP 2 (conversion of sodium chromate into sodium dichromate) The sodium chromate solution obtained in step 1 is treated with concentrated sulphuric acid. Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl (b) Explain why transition metals form many co-ordination complexes. Potassium dichromate being less soluble crystallizes out on cooling. 2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O On concentration less soluble sodium sulphate (Na2SO4. [3] ANSWER STEP 1 (preparation of sodium chromate) Finely powdered chromite ore is mixed with soda ash and quicklime. Yellow mass due to the formation of sodium chromate is obtained. The sodium chromate is converted into sodium dichromate. 4FeCr2O4 + 8Na2CO3 + 7O2 → 2Fe2O3 + 8CO2(g) + 8Na2CrO4 The yellow mass is extracted with water and filtered. This is filtered hot and allowed to cool.Cl Co Cl Cis NH3 NH3 NH3 Co Cl Trans Cl NH3 (d) Write the formula of potassium trioxalatoferrate (III). [2] ANSWER 11 . STEP 3 (conversion of sodium dichromate to potassium dichromate) Hot concentrated solution of sodium dichromate is treated with a calculated amount of potassium chloride. The filtrate contains sodium chromate.2H2O separates out on standing. This mixture is roasted in a reverberatory furnace in the presence of air.

HCl | propylene Br KOH (aq) CH3CHCH3 | OH isopropyl alcohol 12 .It is due to 1) small size and high nuclear charge of the transition metal cations. 2) The availability of vacant inner d-orbitals of suitable energy. ANSWER [2] Methyl amine HNO2 P/I2 NH CH3I CH3 2 CH3OH Methyl alcohol Methyl iodide H2 CH3CH2NH2 Ethyl amine /Ni CH CN 3 KCN Methyl cyanide (ii) Propanol to isopropyl alcohol [2] CH3CH2CH2OH propanol SOCl2 propyl chloride CH3CH2CH2Cl isopropyl bromide HBr alc.KOH CH3CHCH3 CH3CH CH2 . SECTION C (Answer any two questions) Question 8 (a) How can the following conversions be brought about? (i) Methyl amine to ethylamine.

What is its structural formula? [1] CH3 H C Cl Cl CH3 C C2H5 mirror l-isomer H C 2 H5 d-isomer 13 .(iii) Acetaldehyde to Acetone. O + CH3 Mg Br CH3 C | H acetaldehyde CH3 | C isopropyl alcohol | H CH3 OH CH3 C O Mg Br | H OH H [2] K2Cr2O7 CH3 H + C CH3 acetone O (b) Name the organic compounds which have the same molecular formula C2H6O. Write the reactions of these two compounds with PCl5 [3] i) C2H5OH ethyl alcohol ii) CH3-O-CH3 dimethyl ether ANSWER i) C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl ii) CH3-O-CH3 + PCl5 → 2CH3Cl + POCl3 (c)An alkyl halide having the molecular formula C4H9Cl is optically active.

I2 Alc. B. [2] LiAlH4 Red P.Question 9 (a) Identify the compounds A. I2 Alc. H 2O H + . CH3COOH ⎯⎯⎯⎯⎯ A ⎯⎯⎯⎯⎯⎯ B ⎯⎯⎯⎯⎯⎯ C → → → ⎯⎯⎯⎯⎯ D → LiAlH4 Red P. (c) Fill in the blanks and name the following reactions. (ii) On adding freshly prepared pyrogallol solution containing excess of HCl to formaldehyde solution a white precipitate is formed which soon acquires pink colour. KCN H + . H 2O ANSWER (i) Phenol gives violet colour with neutral ferric chloride solution while benzoic acid gives buff coloured precipitate Or benzoic acid gives carbon dioxide gas with sodium bicarbonate while phenol does not. Acetaldehyde will not answer this test. C and D. (ii) Formaldehyde and Acetaldehyde. KCN H + . 14 [3] . H 2O [2] ANSWER: CH3COOH ⎯⎯⎯⎯⎯ CH3CH2OH (Ethanol) [A] → CH3CH2OH (Ethanol) [A] ⎯⎯⎯⎯⎯⎯ CH3CH2I (Ethyl iodide) [B] → CH3CH2I (Ethyl iodide) [B] ⎯⎯⎯⎯⎯⎯ CH3CH2CN (Ethyl cyanide) [C] → CH3CH2CN (Ethyl cyanide) [C] ⎯⎯⎯⎯⎯ CH3CH2CONH2 (Propanamide) → CH3CH2CONH2 (Propanamide) ⎯⎯⎯⎯⎯ CH3CH2COOH (Propanoic acid) [D] → (b) Give one good chemical test to distinguish between the following pairs of compounds (i) Benzoic acid and phenol.

ANSWER (i) Phenol ionizes in water to give phenoxide ion and H+ ion. Resonance structures of phenol Resonance structures of phenoxide ion 15 .+ HCl → (iii) + ANSWER (i) C6H5NC Carbylamine reaction reaction (iii) Benzoylation reaction or Schotten Baumann reaction (d) Give reasons for the following: (i) Phenol is acidic but ethanol is not. ⎯⎯ -------.(i) CH3NH2 + CHCl3 + 3KOH(alc). [3] (ii) C6H5CHO Rosenmund’s Δ Pd/BaSO4 Phenol as well as phenoxide ion are stabilized by resonance.+ KCl + 3H2O → (ii) C6H5COCl + H2 ⎯⎯⎯⎯⎯⎯ -------.

Only aldehydes having no alpha hydrogen undergo the Cannizzaro’s reaction. Therefore the equilibrium move to the dissociated form and hence phenol furnish a high concentration of H+ ions and behave as fairly strong acid In the case of ethanol neither ethanol nor ethoxide ion is stabilized by resonance and hence it behaves as weaker acid than phenol. ANSWER Acetaldehyde contains alpha hydrogen atom. The 16 . So they undergo Cannizzaro’s reaction.Phenoxide is more stabilized by resonance than phenol. CH3CHO has 3 alpha hydrogen. Formaldehyde and benzaldehyde have no alpha hydrogen atom. To determine the primary structure of a protein it is hydrolysed and the amino acids formed are identified. The sequence in which amino acids are arranged in a protein is called its primary structure. The nature and quantity of each amino acid produced due to hydrolysis can be used to establish the sequence of amino acids in the protein chain. C2H5OH C2H5O. Hydrogen attached to the alpha carbon (carbon attached to the functional group) is called alpha hydrogen. (Reason: In phenol. three contributing structures involve charge separation whereas in case of phenoxide ion there is no charge separation). Question 10 (a) What are proteins? How are they formed? What is the primary structure of proteins [3] ANSWER Proteins are complex nitrogenous organic compounds which are essential for the growth and maintenance of life. Proteins perform many biological functions. They are formed by the condensation polymerization of alpha amino acids through the formation of peptide bonds ( [-CO-NH-] linkage).+ H+ Ethanol Ethoxide ion (ii) Acetaldehyde does not give Cannizzaro’s reaction but formaldehyde and benzaldehyde give the reaction. Proteins are polypeptides of very high molecular mass. So it does not undergo Cannizzaro’s reaction.

(C) reduces Tollen’s reagent to give silver mirror and (D). Identify (A). CH3CHO + 2Ag[(NH3)2]OH CH3COOH + 4NH3 + H2O + 2Ag (silver mirror) 17 . (ii) Nylon – 66. (D) on reacting with Phosphorous pentachloride followed by ammonia gives (E). (E) on dehydration produces methyl cyanide. (D) and (E) and write the relevant reactions. (B). (A) on mild oxidation gives (C). (b) Give the monomers of: (i) Bakelite.amino acid sequence in a protein determines its function. (C). [5] ANSWER The reactions suggest that [A] is C2H5OH Acetaldehyde reduces Tollen’s reagent. ANSWER (i) Phenol and formaldehyde (ii) Adipic acid and hexamethylenediamine [2] (c) An organic compound (A) on treatment with acetic acid in the presence of Sulphuric acid produces an ester (B).

CH3COOH + PCl5 [D] Acetic acid HCl+ CH3CONH2 [E] Acetamide P2O5 Heat CH3COCl + POCl3+ HCl NH3 CH3CN + H2O Methyl cyanide 18 .

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