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

3. Hydrate isomerism.

4. Geometrical isomerism.

(ii) Cannizzaros reaction is given by: 1. Formaldehyde 2. Acetaldehyde. 3. Acetone. 4. Ethanol. (iii) Out of the following solutions, the one having the highest boiling point will be: 1. 0.01 M Na2SO4 . 2. 0.01 M KNO3 . 3. 0.01 M Urea. 4. 0.01 M Glucose. (iv) The bond angle of water is: 1. 90o 2. 105o o 3. 107.3 4. 120o (v) The co-ordination number of each ion in copper crystals is: 1. four 2. twelve 3. fourteen 4. eight ANSWER (i) ionization isomerism (ii) Formaldehyde (iii) 0.01M 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 0.0123 C. 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. (iii) Express the relationship between molar conductivity and specific conductivity of a solution. 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. (v) How is the free energy change related to the enthalpy and entropy change of a substance? ANSWER (i)

Tf for NaCl = 0.0123oC NaCl(s) + aq = Na+(aq) + Cl-(aq) 1 mol 1mol 1mol

In solution the number of particles is doubled. So the colligative properties are also doubled. For normal molecules like glucose Tf will not be doubled. So Tf for glucose =

0.0123 o = 0.00615 C 2

(ii) There is no change in the pH value of the solution. 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

base (iii)

k x 1000 Molarity m = molar conductivity k = specfic conductivity Unit of molar conductivity = ohm-1 cm2 mol-1 m =
(iv)

At anode Zn(s) Zn2+ + 2eAt cathode 2Ag+(aq) + 2e- 2Ag(s)

(v)

G = H - T S G = Free energy change at constant T and P H = Enthalpy change S = Entropy change T = Absolute temperature
[5]

(d) Match the following: (i) Buffer solution (a) Co-ordinate bond (ii) Co-ordination compounds (b) Raoults Law (iii) Dilute solution (c) Warners Theory (iv) Ammonium ion (d) Faradays Law (v) Electrolysis (e) Hendersons equation ANSWER (i) Buffer solution (e) Hendersons equation (ii) Co-ordination compounds (c) Warners Theory (iii) Dilute solution (b) Raoults Law (iv) Ammonium ion (a) Co-ordinate bond (v) Electrolysis (d) Faradays Law PART II Answer six questions choosing two from Section A, two from Section B and two from Section C. SECTION A (Answer any two questions) Question 2 3

(a) (i) The vapour pressure of pure benzene at a certain temperature is 640 mm Hg. When a non-volatile and non-electrolyte solid weighing 2.175 g is added to 39.0 g of benzene, the vapour pressure of the solution is 600 mm Hg. 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) = 2.175g Mass of solvent (W) = 39g Molecular mass of solvent benzene (C6H6) (M) = 78 For a very dilute solution po - p wM = o p Wm m is the molecular mass of the solid substace (solute) m= m= wM po W po p 2.175 x 78 640 640 600 = 69.6 39

(ii) Calculate the standard enthalpy change for a reaction CO2(g) + H2(g) CO(g) + H2O(g). Given that Hfo for CO2(g), CO(g) and H2O(g) are 393.5, 110.5, and 248 KJ mol-1 respectively. [3] ANSWER

Horeaction = Hfo(products) - Hfo(reactants) Horeaction = -110.5 + (-244.8) - (-393.5) = -355.3 + 393.5 = 38.2 kJmol-1
(b) Give reasons for the following: (i) A solution of copper sulphate is acidic in nature. [2] ANSWER Copper sulphate is a salt of strong acid H2SO4 and a weak base Cu(OH)2.It dissociates almost completely in aqueous solution into Cu2+ and SO42- ions. 4

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.

2H2O 2H+ + 2OHCu2+ + 2OHCu(OH)2

In order to compensate the decrease of OH- ions the undissociated water molecules dissociate to keep the value of Kw constant. This increases the H+ ion concentration in solution. Hence the solution becomes acidic. (ii) The boiling point of p-nitrophenol is more than that of o - nitrophenol. [2] Ortho nitrophenol possesses intramolecular hydrogen bonding.Assication of molecules does not take place. Their molecular weight remains the same and hence boiling point does not increase too much. Paranitrophenol possesses intermolecular hydrogen bonding. Association of molecules takes place. Their molecular weight increases and hence boiling point increases.

Question 3 (a) (i) An element crystallizes in a structure having F.C.C. unit cell of an edge 200 pm. Calculate its density if 200g of this element contains 24 x 1023 atoms. [3] ANSWER

=
M=

200 x 6.023 x 1023 = 50.19 24 x 1023 4 x 50.19 = 41.66 g/cm3 = -10 3 23 ( 200 x 10 ) x 6.023 x 10

Zm a3 N o

(ii) Draw the electron dot structure of perchloric acid clearly distinguishing between the electrons of each atom. [1] 5

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.

Ea = Et - 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.

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. The slope of the line is equal to Ea/2.303 R. So the activation energy Ea can be calculated. (ii) Consider the following data for the reaction A + B Products. [3] Conc. of A (mol l-1) Conc. of B (mol l-1) Initial rate (mol l-1 S-1) 0.1 0.1 4.0 x 10-4 0.2 0.2 1.6 x 10-3 0.5 0.1 1.0 x 10-2 0.5 0.5 1.0 x 10-2 Calculate: 6

(1) The order with respect to A and B for the reaction. (2) The rate constant of the reaction. ANSWER (i) Suppose the order with respect to A is p and with respect to B is q. Then the rate law is: rate = k [A]p [B]q Substituting the values from experiment 4.0 x 10-4 = k [0.1] p [0.1] q ---------------------equation 1 1.6 x 10-3 = k [0.2] p [0.2] q ---------------------equation 2 1.0 x 10-2 = k [0.5] p [0.1] q ---------------------equation 3 1.0 x 10-2 = k [0.5] p [0.5] q--------------------- equation 4 Dividing equation 1 by equation 3
p k 0.1 0.1 4.0 x 104 0.1 = p q = 1.0 x 102 0.5 k 0.5 0.1 0.04 = [0.2]p log 0.04 = p log 0.2 log 0.04 p= =2 log 0.2 order with respect to A is 2 p q

Dividing equation 3 by equation 4

k 0.5 0.1 1.0 x 102 = p q 1.0 x 102 k 0.5 0.5

0.1 1= 0.5
q

log 1 = q log 0.2 log 1 q= =0 log 0.2

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 4.0 x 104 = = 0.04 L/mol/s [A]2 0.1 x 102

Question 4 (a) (i) What is the type of hybridization in PCl5 molecule? Explain why PCl5 is very 7

reactive in nature. ANSWER Sp3d hybridization ( Trigonal bipyramidal hybridization ) The five hybrid orbitals are not equivalent.

[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. (ii) If 100 ml. of 0.1 M CH3COOH is mixed with 200 ml of 0.5 M CH3COONa, 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 p = - log 1.8 x 10-5 + log10
10 H

p = - log 1.8 x 10-5 + log10

10 H

0.1x100 ] 1000 0.5 x 1000 [ ] 200 [0.01] [2.5] [

p = 4.745 + ( 2.3979) = 2.3471

b) Give reasons why: [5] (i) Aluminium trichloride exists as a dimmer. (ii) When H2S is passed through a solution of acidified copper nitrate and zinc nitrate, only copper is precipitated as sulphide 8

ANSWER (i) In AlCl3 aluminium atom has only 6 electrons in its outermost shell. To achieve octet ie.to achieve stability the molecule exists as dimer.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. Thus both aluminium atoms in the dimer achieve octets.

. ANSWER (ii) The solubility product of sulphide of copper is very low.(cations of group II). 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. In acid medium the dissociation of H2S is suppressed due to common ion effect.

H2S HCl

2H+ + S2H+ + Cl-

(acid) So the sulphide ion concentration is low. This is enough to exceed the very low Ksp of CuS. So it gets precipitated. The sulphide ion concentration is not enough to exceed the very high Ksp of ZnS. So it is not precipitated. SECTION B (Answer any two questions) Question 5 (a) Explain how fluorine is prepared by the electrolysis of potassium hydrogen fluoride. [3] In Whytlaw Grays method fluorine is prepared by the electrolysis of fused KHF2. The apparatus consists of an electrically heated copper vessel which acts as the cathode.A pure graphite rod is used as anode. The graphite rod is enclosed in a copper diaphragm perforated at the bottom. The diaphragm prevents the mixing of hydrogen liberated at the cathode and fluorine liberated at the anode. KHF2 KF + HF HF H+ + FAt cathode: 2H+ + 2e- H2 9

At anode: 2F- - 2e- F2 Fluorine is liberated at anode and is stored in steel cylinders. (b) Give balanced equations for each of the following reactions: (i) Fluorine and dilute NaOH. (ii) Ozone and aqueous potassium oxide. [2] ANSWER (i) 2F2 + 2NaOH 2NaF + H2O + OF2 (oxygen difluoride) (ii) K2O + H2O 2KOH 2KOH + 5O3 2KO3 + 5O2 + H2O KO3 is potassium ozonide. It is orange coloured solid and contains the paramagnetic O3- ion. Question 6 (a) Name the following compounds according to I.U.P.A.C. 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- ion when dissolved in water. K4 [Fe (CN) 6]

H2 O

4K+ + Fe [(CN) 6]4-

Ferrocyanide ion is a complex ion and does not ionize into constituent ions. So it does not give the usual tests for Fe2+ ion. (c) Draw the geometrical isomers of the compound [Co (NH3)2 Cl2] [1] ANSWER

10

Cl Co Cl Cis

NH3 NH3

NH3 Co Cl Trans

Cl NH3

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

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. SECTION C (Answer any two questions) Question 8 (a) How can the following conversions be brought about? (i) Methyl amine to ethylamine. 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 - HCl | propylene Br KOH (aq) CH3CHCH3 | OH isopropyl alcohol
12

(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

(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. What is its structural formula? [1]

CH3 H C Cl Cl

CH3 C C2H5
mirror l-isomer

C 2 H5
d-isomer

13

Question 9 (a) Identify the compounds A, B, C and D. CH3COOH A B C

D

LiAlH4

Red P, I2

Alc. KCN

H + , 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. (ii) Formaldehyde and Acetaldehyde. [2]

LiAlH4

Red P, I2

Alc. KCN

H + , H 2O

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. (ii) On adding freshly prepared pyrogallol solution containing excess of HCl to formaldehyde solution a white precipitate is formed which soon acquires pink colour. Acetaldehyde will not answer this test. (c) Fill in the blanks and name the following reactions. 14 [3]

(i) CH3NH2 + CHCl3 + 3KOH(alc). -------- + KCl + 3H2O (ii) C6H5COCl + H2 -------- + 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. ANSWER (i) Phenol ionizes in water to give phenoxide ion and H+ ion. [3] (ii) C6H5CHO Rosenmunds

Pd/BaSO4

Phenol as well as phenoxide ion are stabilized by resonance. Resonance structures of phenol

Resonance structures of phenoxide ion 15

Phenoxide is more stabilized by resonance than phenol. (Reason: In phenol, three contributing structures involve charge separation whereas in case of phenoxide ion there is no charge separation). 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. C2H5OH C2H5O- + H+ Ethanol Ethoxide ion (ii) Acetaldehyde does not give Cannizzaros reaction but formaldehyde and benzaldehyde give the reaction. ANSWER Acetaldehyde contains alpha hydrogen atom. Hydrogen attached to the alpha carbon (carbon attached to the functional group) is called alpha hydrogen. CH3CHO has 3 alpha hydrogen. So it does not undergo Cannizzaros reaction. Formaldehyde and benzaldehyde have no alpha hydrogen atom. So they undergo Cannizzaros reaction. Only aldehydes having no alpha hydrogen undergo the Cannizzaros reaction. 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). Proteins are polypeptides of very high molecular mass. The sequence in which amino acids are arranged in a protein is called its primary structure. To determine the primary structure of a protein it is hydrolysed and the amino acids formed are identified. 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. The 16

amino acid sequence in a protein determines its function. (b) Give the monomers of: (i) Bakelite. (ii) Nylon 66. 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). (A) on mild oxidation gives (C). (C) reduces Tollens reagent to give silver mirror and (D). (D) on reacting with Phosphorous pentachloride followed by ammonia gives (E). (E) on dehydration produces methyl cyanide. Identify (A), (B), (C), (D) and (E) and write the relevant reactions. [5] ANSWER The reactions suggest that [A] is C2H5OH

Acetaldehyde reduces Tollens reagent.

CH3CHO + 2Ag[(NH3)2]OH

CH3COOH + 4NH3 + H2O + 2Ag (silver mirror)

17

CH3COOH + PCl5 [D] Acetic acid HCl+ CH3CONH2 [E] Acetamide P2O5 Heat

CH3COCl + POCl3+ HCl NH3

CH3CN + H2O Methyl cyanide

18