2. Class: XII SESSION : 2022-2023 SUBJECT: Chemistry (043) SAMPLE QUESTION PAPER - 5 with SOLUTION MM: 70 Time: 3 hours General Instructions: Read the following instructions carefully. a) There are 35 questions in this question paper with internal choice. b) SECTION A consists of 18 multiple-choice questions carrying 1 mark each. ©) SECTION B consists of 7 very short answer questions carrying 2 marks each. 1d) SECTION C consists of 5 short answer questions carrying 3 marks each. ©) SECTION D consists of 2 case- based questions carrying 4 marks each. ) SECTION E consists of 3 long answer questions carrying 5 marks each. 9) All questions are compulsory. h) Use of log tables and calculators is not allowed Section A ‘What is the structural formula of the monosaccharide that is used in Kiliani-Fischer synthesis of: CHO u—t—on °) d) Go H—}—on HO—}— Ho—}-—H HO—}—H CHO cH,OH H—}-—on Which of the following arrangements does not represent the eorreet order of the property stated against it? a) y2+ < 2+ P>Q>R b)Q>P>S>R c)Q>P>R>S d)P>Q>R>S e.m.f, ofa cell in terms of the reduction potential of its left and right electrode is: a)E=ER-EL b) E=-[ER +E] o)E=EL+ER d)E=EL-ER Fusion of chromite ore with sodium carbonate in excess of air gives a compound (X) (yellow solution) X when treated with sulphuric acid gives: a) Na2Cr207 b) NagCr207 - 5H20. c) NagCr907 - 1020. d) NayCr207 - 2H20. Which of the following compound will not give Cannizzaro’s reaction?a) CH3CHO b) HCHO ©) C6HsCHO 4) (Me)3CCHO a)+k b)-k k 9 Se 3-Pentanol is an example of: a) Primary alcohol b) Secondary alcohol ©) Tertiary aleohol 4d) Aromatic aleohol The standard reduction potentials at 25°C of Li*|Li, Ba2*|Ba, Na*[Na and Mg?*|Mg are -3.05, -2.73, -2.71 and -2.37 V respectively. Which is strongest reducting agent? a)Mg b) Na Li @)Ba Identify Z in the following reaction sequence Mo ice | (PHC, CI — XY —42 Ether Dry (i) H,0 a) CH3Megl b) CH3COCI ©) CICH)COOH 4) CH3COOH Methyl- @-D-glucoside and methyl- §-D-glucoside are a) Enantiomers b) Anomers ¢) Conformational diastereomers) Epimers Assertion (A): N-Ethylbenzene sulphonamide is soluble in alkali. Reason (R): Hydrogen attached to nitrogen in sulphonamide is strongly acidic. a) Both A and Rare trueand Ris) Both A and R are true but R is the correct explanation of A. not the correct explanation of A. c) Ais true but R is false. d) A is false but R is true. Assertion (A): The complex ion trans-[Co(en)2CIg]* is optically active. Reason (R): It is an octahedral complex. a) Both A and Raretrueand Ris b) Both A and R are true but R is the correct explanation of A. not the correct explanation of A.c) A is true but R is false. d) A is false but R is true. Assertion (A): Ether behaves as bases in the presence of mineral acids. Reason (R): Due to the presence of lone pairs of electrons on oxygen. a) Both A and Rare true and Ris) Both A and Rare true but R is the correct explanation of A. not the correct explanation of A. c) Ais true but R is false. d) A is false but R is true. Assertion (A): Cu2* iodide is not known. Reason (R): Cu2* oxidises I” to iodine. a) Both A and R are true and R is b) Both A and R are true but R is the correct explanation of A. not the correct explanation of A. ©) Ais true but R is false, 4d) A is false but R is true. Section B Resistance of a conductivity cell filled with 0.1 mol L“! KCI solution is 100Q.1f — [21 the resistance of the same cell when filled with 0.02 mol L*! KCI solution is 520 a, calculate the conductivity and molar conductivity of 0.02 mol L7! KCI solution. The conductivity of 0.1 mol L"! KCI solution is 1.29 S/m. OR i. Write anode and cathode reactions that occur in dry cell. ii, How does a dry cell differ from a mereury cell? State the ‘rate law' for chemical reactions. When a coordination compound CoCl3 -6NH3 is mixed with AgNO3, 3 moles of AgC! are precipitated per mole of the compound. Write i, structural formula of the complex. ii, IUPAC name of the complex. OR How is stability of coordination compounds determined in aqueous solution? Why is osmotic pressure of 1 M KCI higher than that of | M urea solution? In fig, identify the nature of electrolyte A & B. In which case it is not possible toobtain value of limiting molar conduetance? Ortho-nitrophenol is more acidic than ortho-methoxyphenol. (reason) Draw the structure of the major monohalo product in the following reaction : Section C Write reactions for the conversion of: i, Aniline to benzene ii, Methyl amine to methyl cyanide iii, Propanenitrile to ethylamine. Calculate the emf of the following cell: Mg(s)/Mg2*(0.2M) || Ag*(1 x 10°3M) | Ag(s) E%Ag*/Ag) = 0.80V £(Mg?*/Mg) = -2.37V Give reasons for the following: a. Transition metals form complex compounds. b. Eo values for (Zn2*/Zn) and (Mn2+/Mn) are more negative than expected. c. Actinoids show wide range of oxidation states. Why is sulphuric acid not used during the reaction of alcohols with KI? BI OR Discuss the role of Lewis acids in the preparation of aryl bromides and chlorides in the dark. ‘The rate of a particular reaction triples when temperature changes from 50°C to 13] 100°C. Calculate the activation energy of the reaction. [Given log 3 = 0.4771; R= 8.314 K! mot” !] Section D Read the text carefully and answer the questions: Pentose and hexose undergo intramolecular hemiacetal or hemiketal formation due to combination of the -OH group with the carbonyl group. The actual structure is either of five or six membered ring containing an oxygen atom. In the free state all pentoses and hexoses exist in pyranose form (resembling pyran). However, in the combined state some of them exist as five membered cyclic structures, called fiiranose (resembling furan).a Gi) The eyclie structure of glucose is represented by Haworth strueture: ‘CH,OH “CH,OH —9OH H f-—0, OH we VYOH HO e OH e-D-4+)-Glucopyranose PLD) a. and 8-D-glucose have different configurations at anomeric (C-1) carbon atom, hence are called anomers and the C-1 carbon atom is called anomeric carbon (glycosidic carbon). ‘The six-membered cyclie structure of glucose is called the pyranose structure. What percentage of 8-D-(+) glucopyranose is found at equilibrium in the aqueous solution? The following carbohydrate is OH F Oo HO HO: H HOHE QoH | Inthe carbon structure, «( pi)! anomeric carbon is OR What are a-D(+)-glucose and -D(+)glucose? Read the text carefully and answer the questions: Isomers are two or more compounds that have the same chemical formula but a different arrangement of atoms. Due to the different arrangements of atoms, they differ in one or more physical or chemical properties. Two principal types of isomerism are known among coordination compounds. Stereoisomerism includes geometrical isomerism, optical isomerism while Structural isomerism consists of linkage isomerism, coordination isomerism, lonisation isomerism and Solvate isomerism. Isomerism arises in heteroleptic complexes due to different possible geometric arrangements of the ligands, In a square planar complex of formula [MX2L3] X and L are unidentate, the two ligands X may be arranged adjacent to each other in a cis isomer, or opposite to each other in a trans isomer. Solvate form of isomerism is known as ‘hydrate isomerism’ in the case where water is involved as a solvent. This is similar to ionisation isomerism. Optical isomers are called chiral. Explain Draw one of the geometrical isomers of the complex [Pt(en)2Cl9|2* which isoptically active. (iii) Why thiocyanate is an ambidentate ligand? OR Why molecular shape of Ni(CO)4 is not the same as that of INi(CN)4]?°? Section E An alkene A (Mol. formula CsH 9) on ozonolysis gives a mixture of two compounds B and C. Compound B gives positive Fehling’s test and also forms iodoform on treatment with I and NaOH. Compound C does not give Fehling’s test but forms iodoform. Identify the compounds A, B and C. Write the reaction for ozonolysis and formation of iodoform from B and C. OR a, Write the main product formed when propanal reacts with the following reagents: i, 2 moles of CH3OH in presence of dry HCI ii, Dilute NaOH iii, HN — NH followed by heating with KOH in ethylene glycol b. Arrange the following compounds in increasing order of their property as indicated : i, F -CH2COOH, ODN - CH2COOH, CH3COOH, HCOOH - acidie character ii, Acetone, Acetaldehyde, Benzaldehyde, Acetophenone - reactivity towards addition of HCN State Raoult’s law for a solution containing volatile components. What is the 15] similarity between Raoult’s law and Henry's law? OR ‘What is meant by positive and negative deviations from Raoult's law and how is the sign of Amixll sol related to positive and negative deviations from Raoult's law? Answer the following questions: 15] How would you account for the following? Among lanthanoids, Ln (III) compounds are predominant. However, occasionally in solutions or in solid compounds, +2 and +4 ions are also obtained. Convert: Benzene to o-chlorotoluene. Write the structure of the compound whose IUPAC name is: 2-Methylbutane - 2 -ol Why does NH3 act as a Lewis base? Deficiency of which vitamin causes scurvy?SOLUTION Section A Ho—j—n Explanation: a——ou cron 2. (a) V2* < Cr2* < Mn? < Fe2* : paramagnetic behaviour Explanation: V2+ < Cr2* < Mn2 < Fe2* : paramagnetic behaviour i 3. (b) CHy ~ CH, ~C~ CH Explanation: The product obtain is HH CH3CH,C = CH+H,0 "5 CHsCHLC =CH, = CHsCHaC — CH; “ oD ° Ph Sam we planation: Ph 5. (a) Elementary reaction Explanation: An elementary reaction is a chemical reaction in which one or more chemical species react directly to form products in a single reaction step and with a single transition state. 6.(c)Q>P>R>S Explanation: Q is most basic as it is an aliphatic amine, P is more basic than R and S as Ip © of P is delocalize. 7.(a) E= BR - EL, Explanation: Ecol] = Bor, + Err,-—Bav, + Burg 8. (d) NagCr207 - 220 Explanation: 4FeCr20q + 8NagCO3 + 702 —> 8Na7Cr04 + 2Fe203 + 8CO2 2NagCrOq + 2H* —+ NagCr707 + 2Na* +0. 9. (a) CH3CHO Explanation: Cannizzaro reaction is given by aldehydes that do not contain an alpha hydrogen atom. In this reaction, a molecule of carbonyl compound is oxidized to carboxylic acid and another molecule is reduced to an alcohol. Acetaldehyde does not give Cannizaro's reaction as it contains an alpha hydrogen atom. Instead, it undergoes the aldol condensation reaction.10. (b) -k Explanation: Slop of the line indicates = -k while the intercept represents [R]o. . (b) Secondary aleohol Explanation: Secondary alcohol is a compound in which a hydroxy group, OH, is attached fo a saturated carbon atom which has two other carbon atoms attached to i non on oH oH mb bbw Hoh on Hon (©) Li Explanation: 13, for Li is more, Li Lite Thus, Li is strong oxidant. 3. (¢) CICH2COOH Explanation: CICHCOOH . (b) Anomers Explanation: Methyl-a-D-glucoside and methy|-B-D- glucoside differ at C-1, hence are called anomers iy /oc, Oct. i Ctl ge G0 j cyon con Maya Dganide Met sluice (a) Both A and R are true and R is the correct explanation of A. Explanation: C2H5, ay —SO_CgH; + NaOH - CoH; —N—SO,CsH; + H2O Soluble sale a Ethylbezene sulphonamide Ethylbenzene sulphonamide is soluble in alkali because it has acidic hydrogen. . (b) Both A and R are true but R is not the correct explanation of A. Explanation: Both A and R are true but R is not the correct explanation of A. (a) Both A and R are true and R is the correct explanation of A. Explanation: Both A and R are true and R is the correct explanation of A. . (a) Both A and R are true and R is the correct explanation of A. 2 Explanation: Cu oxidizes iodide to iodine hence cupric iodide is converted to cuprous iodide. Section B . The cell constant is given by the equation: Cell constant = G* = conduetivity resistance = 1.29 Sim x 100 2= 129 mr! = 1.29 em"! Conductivity of 0.02 mol L7! KCI solution = cell constant / resistance = 129m al aoa = 0.248 Sm Concentration = 0.02 mol L*! = 1000 x 0,02 mol m3 = 20 mol m> Molar conductivity = Am = 4 = 28t0-*8* = 124 x 104 § m?mot"! Alternatively, conductivity of solution K = 422%" == 0.248 x 10° § em"!and molar conductivity of solution Ay, =K x 1000 cm? L*! molarity"! (0.24810 Sem 1000¢mn E- 0.02molL-! = 124 Sem? mot! i, Reactions in dry cell: At Anode: Znjs) + Zint?* + 207 At Cathode: MnO + NHg* + ¢” > MnO(OH) + NH3 ii, Dry cell has shorter life than mercury cell, Cell potential in mercury cell remains constant but not in dry cell. ). Rate law is the expression in which reaction rate is given in terms of molar concentration of reactants with each term raised to some power, which may or may not be same as the stoichiometric coefficient of the reacting species in a balanced chemical equation. For the reaction: aA +bB —+ oC + dD, the rate law is: Rate = k [AP* [B]¥ ; where a may or may be ‘equal to x; and b may or may be equal to y. Rate law is experimentally determined. i, When one mole of CoCl3.6NH3 is mixed with AgNO3, three moles of AgCl are precipitated which indicates that three ionisable chloride ions in the complex are present. Hence, its structural formula is [Co(NH3)6]C13. ii, TUPAC name of the complex [Co(NH3)6]Cl3 is Hexa ammine cobalt (III) chloride. OR The stability of coordination compound is measured in terms of stability constant. ‘Thus if we have a reaction of the type M+4L= ML, — tty) Pa Taos . 1 M KCI solution dissociates in solution to give K* and CI’ ions. KCL K* +Cl- Therefore its osmotic pressure (which depends on number of solute particles) is higher than that of 1 M solutions of urea which does not dissociate or associate in solution. . A = strong Electrolyte. B = weak Electrolyte. In case of B, it is not possible to get an exact value of limiting molar conductance. . It is because nitro group is electron withdrawing which increases acidic character due to 25. stabilization of o-nitrophenoxide ion whereas -OCH3 group is electron releasing which decreases acidic character due to destabilization of o-methoxy phenoxide ion. CHOH chal HO" HO" “Hydeonymethlohenel “Chloromethyphencl Section C NH; ‘Oa Om Jee i ii. HCN Fy S cHon CHC” CHC = N° Nt on Bry ili, CHyCH)CN + HO —>CH,CH) ~ C— NH, —> CH;CIbNIy HyO; ‘KOH — Ethanamine Mes) —> Mg" (aq) + 26” t ‘Ag’ (aq) + 2e° —+ 2 Ag(s) Mg(s) + 2Ag" (aq) —+ Mg*"(aq) + 2Ag(s) applying nernst equation oa — Ey ~ Mog ML E%(Ag* / Ag) — E(Mg?* /Mg) — Sloss = +0.80V — (—2.37V) — 294 Jog(2 x 10°) +3.17V — 2951 [log 2 + log 10°] +3.17V — 20881 x 5.3010 17V -0.1566V 0134 V . Transition metals form complex compounds due to small size, high ionic charge and availabilty of d-orbital. |. Eg values for (Zn2*/Zn) and (Mn2+/Mn) are more negative than expected due to stable 3d! configuration in Zn2* and 35 configuration in Mn2*. . Actinoids show wide range of oxidation states due to comparable energies of Sf ,6d and 7s orbitals. ). In the presence of sulphuric acid (H2S04),KI produces HI 2KI + HpS0q -+ 2KHSOq + 2HI Since HS04 is an oxidizing agent, it oxidizes HI (produced in the reaction to 19). 2HI + H9SO4 > In + S07 + HO Asa result, the reaction between alcohol and HI to produce alkyl iodide cannot occur. Therefore, sulphuric acid is not used during the reaction of alcohols with KI. Instead, a non-oxidizing acid such as H3POg is used. OR Aryl bromides and chlorides can be prepared from arenes by electrophilic substitution reaction by Chlorine and Bromine respectively. This reaction is carried out by treating the arene with chlorine or bromine in the presence of iron (III) chloride in the absence of light. Iron (III) chloride, that is, FeCl3 is a Lewis acid, which generates the electrophile required to take the reaction forward. FeCl3 forms a coordination compound with Cla, making the complex CI*[FeClq"]. The chloride ion gains a partial positive charge, acting as an electrophile, and attacking the « bonds. The final products are o-aryl halide and p-aryl halide isomers which can be separated easily. Hs im Hs CH —_=_, +e dark + x x o-halotoluene prhalotoluene 30. T)= 273 + 50=323K T= 273 + 100 = 373 KUsing the formula, Be [Tet bog = sa [SE] sta = saunion [Som Bax80 log3 = raaEsin aa B, = 22011.76 Jmol Section D 31, Read the text carefully and answer the questions: Pentose and hexose undergo intramolecular hemiacetal or hemiketal formation due to combination of the -OH group with the carbonyl group. The actual structure is either of five or six membered ring containing an oxygen atom. In the free state all pentoses and hexoses exist in pyranose form (resembling pyran). However, in the combined state some of them exist as five membered cyclic structures, called fiiranose (resembling furan). | i) oO oO Pyrn Furan The cyclic structure of glucose is represented by Haworth structure: ‘CH,OH ‘CH,OH H /-—0, OH H } ‘Non H/\" YOH HO H +h sp H OH H OH a@-D-{*)-Glucopyranose _ -D-(+)-Glucopyranose @ and 6-D-glucose have different configurations at anomeric (C-1) carbon atom, hence are called anomers and the C-1 carbon atom is called anomeric carbon (glycosidic carbon). The six-membered cyclic structure of glucose is called the pyranose structure, (@) Ordinary glucose is e-glucose, with a fresh aqueous solution having specific rotation, [a]p = +111°. On keeping the solution for some time, a-glucose slowly changes into an equilibrium mixture of a-glucose (36%) and 8-glucose (64%) and the mixture has specific rotation + 52.5°. ii) This structure is an example of pyranose and aldohexose. Here, the structure of the carbohydrate is of the B-pyranose form. (iii)C-1 is the anomeric carbon, OR a-D-(+)-glucose and 8-D-(+)-glucose differ in configuration at Cj (ie., anomeric or glycosidic carbon) and hence are called anomers.i Hoe H2c—on © and HOC~H P H4c—on I °cH,0n -D(-}-plucose B-D¢4)-plucose 32. Read the text carefully and answer the questions: Isomers are two or more compounds that have the same chemical formula but a different arrangement of atoms, Due to the different arrangements of atoms, they differ in one or more physical or chemical properties. Two principal types of isomerism are known among coordination compounds. Stereoisomerism includes geometrical isomerism, optical isomerism while Structural isomerism consists of linkage isomerism, coordination isomerism, lonisation isomerism and Solvate isomerism. Isomerism arises in heteroleptic complexes due to different possible geometric arrangements of the ligands. In a square planar complex of formula [MX2L9] X and L are unidentate, the two ligands X may be arranged adjacent to each other in a cis isomer, or opposite to each other in a trans isomer. Solvate form of isomerism is known as ‘hydrate isomerism’ in the case where water is, involved as a solvent. This is similar to ionisation isomerism, (®) Optical isomers are mirror images that cannot be superimposed on one another. While the molecules or ions that cannot be superimposed are called chiral. (i) a a a4 a, Gi)Ppiocyanate ligand, NCS” is present which can bind through the nitrogen to give M- NCS or through sulphur to give M-SCN. oR ‘The molecular shape of [Ni(CO)4] is tetrahedral because this complex nickel involves sp? hybridisation. In [Ni(CN)4]*", nickel involves dsp” and its shape is square planer. Section E 33. Compound B gives positive Fehling's test. It shows that it is an aldehyde and gives an iodoform test which shows it has COCHG group. Compounds C is a ketone because it does not give Febiling's test but gives the iodoform test which shows it also has -COCH3 groups. Hence compound A is CH3CH = C — CH , B is CH3-CHO and compound Cis 0=C(CH3)CH30% i.CH,CH = ie CH, ————> CH, -CHO +O= C -CH; aby (8) Zn/Hj0 — Acetaldehyie a. 2-Methylbut-2-ene @ (Acetone) o other isomers of (A) will not give products corresponding to the given test (2NaOH + Ip —+ NaOl + H30) ii, CHyCHO +3Na0I + ClyCHO+3Na0H ‘Selim om ® te aa Hyirotyis CH,CHO+ NaOH, CHI, + HCOONa Iedoform i i iii, CHy — C-CHy +3NaOI > Cly— CCH, +3NaOH © ‘Po tooacetone i Hortusis CH; ~C—CHs + NaOH ~~~» CHI, +CH;COONa Todoforn Sadun actte OR a. i, CH3CH2CH (OCH3)9 ii, CH3CHQCH (OH) CH (CH3) CHO iii, CH3CH2CH3 b. i, Increasing order of acidic character: CH3COOH < HCOOH < FCH2COOH < 02N-CH2COOH ii, Increasing order of reactivity towards addition of HCN: Acetophenone < Benzaldehyde < acetone < acetaldehyde 34, The partial pressures are related to the mole fractions x and x of the two components 1 and 2 this relation is known as Raoult's law which state that For a solution of volatile liquids: the partial vapour pressure of each component of the solution is directly proportional to its mole fraction present in solution, Thus, for any component, partial ‘vapour pressure, pax p=px Where P° is the vapour pressure of pure component and is the mole fraction of that component. The similarity between Raoult’s law and Henry's law: Both laws state that the partial pressure of the volatile component is directly proportional to its mole fraction in the solution. In the case of Raoult's law, itis liquid and in the case of Henry's law, it is gas. OR According to Raoult’s law, the partial vapour pressure of each volatile component in any solution is directly proportional to its mole fraction. The solutions which obey Raoult’s law over the entire range of concentration are known as ideal solutions. The solutions that do not obey Raoult’s law (non-ideal solutions) have vapour pressures either higher or lower than that predicted by Raoult’ law. If the vapour pressure is higher,(ie A....B interaction is, less than A...A and B...B interaction) then the solution is said to exhibit positive deviation, and if it is lower(A...B interaction is more than A... and B...B interaction), then the solution is said to exhibit negative deviation from Raoult's law.s1=0 Molefracion m= gel me nao ‘Vapour pressure ofa two-component solution showing positive deviation from Raoult’ law | __ Vapour pressure of te slaion | _ Vapour pressure of be wluion a aS Mole faton = 1 nel = get ‘Vapour pressure of a two-component solution showing negative deviation from Raoult’s law. In the case of an ideal solution, the enthalpy of the mixing of the pure components for forming the solution is zero. ASol H= 0. In the case of solutions showing positive deviations, absorption of heat takes place. Therefore, ASol H = Positive In the case of solutions showing negative deviations, evolution of heat takes place. Therefore, ASol H = Negative 35. Answer the following questions: £14 configuration. () 42 and +4 oxidation states are due to high stabilities of £9, £7 and "(Sat + () a cor octane (iii) The structure of 2-Methylbutane - 2 -ol is CH; — é — CH, —CHy on (iv)NH3 act as a Lewis base due to the presence of lone pair of electrons on the nitrogen atom of NH3 molecule. (¥) Vitamin C