ee CALCUTTA UNIVERSITY CHEMISTRY (HONS.) QUESTION PAPERS (PART - | & 11) — 2017 ART —I 5 FIRST PAPER-2017 ion (Group—A) Full Marks — 50 (CHT- 12a) “to Unit-1 Answer any three questions d in 1. @) Are the compounds shown below chiral or achiral 9 Justify 2) your answer, 28, 3 ) of diethyl 2-hydroxy -2, 3-dipheny1 Succinate. How w ill y threo ? (b) Dextro, 3 ‘ng deuteration h loses optical activity dur- 2 rotatory EtCH(Me)Cop! With D,O/Naop. Explain, “Cu, Chem. (Ho; , ns.) (Pare-1& 11 — 201 7-12 C.U. Chemistry Hons. Question Papers (Part-I & II)~2017 4. (a) Assign R/S designation to the following compounds and also show the priority order of the groups : 5 Me CN Cl Ct cl Chr (@) NO,&w7%,-COOH. (ii) “ CH, & CH, (b) Identify the Pro-R and Pro-S hydrogen atoms (underlined) in the following molecules with explanation : COOH @ H H, CH, H, H COOH 5. (a) Find the stereochemical relationship between the two gauche forms (torsion angle + 60°and) of 2R, 3S-butane -2,3-diol, (b) All compounds having enantiotopic ligands are ach ; Justify. ; oa? Unit-II a) Answer any two questions theng i‘ 6. (a) Assign 1-MO energy levels of ‘benzene with the Ti FEE E S First Paper—2017 3 (b) The m.p. of a dicarboxylic acid having even number of car- bon atoms is always higher than that of acids having odd number of carbon atoms lying immediately below or above the series. — Justify and comment. 8 2 7. (a) Justify which compound in each of the following pairs has higher dipole moment : 5 : oO j ae (b) Arrange with reason the following C-C bonds marked ‘a’, ‘b’, and ‘c’ in order of increasing bond length : 2 HC =C*CH =CH*CH,*CH, 8. (a) Bromination of methane is less exothermic than that of chlo- rination. Explain with AH? calculation. Bond energies for C-H = 104, Br— Br=46, H—Br=87.5 Cl-Cl=58, H-Cl= 103, C~Cl=83.5,C-Br=71 kcal/mole respectively. (b) Draw the resonating structures for (i) CHijO— CH=CH -% ® oa CH) and (ii) CH, — C ~eand indicate in each case the relative Contribution of the resonating structures. Z4 C.U. Chemistry Hons. Question Papers (Part-I & II)-2017 (CHT- 12b) 5 Unit-I Answer any three questions 9. (a) Construct a energy profile diagram for a reaction k, k As=B== ! ot 2 in which relative stabilities of three species C>A>B and for which the relative order of rate constant is k,> k >k,>>k (i) How many intermediates are there 2 = (ii) How many transition states are there ? (iii) Which is the rate determining step in forward direction ? 3 2 (b) Of the following two compounds, which one has higher enol content and why ? Pah Pee Ph —CH, - C- CH, = C- CH, and ee lca, Z Ph 10. (a) Arrange the following carbanions in increasing order of sta- bility with justification : (ii) (iii) 3 0 “ oO © oO (b) Account for the pk, values of the following compounds Be Ph,CH - pk, 315 Late Ph oH pk, 18.5 First Paper—2017 5 11. (a)Arrange the following amides in increasing order of basicity. Give reason : F 3 ° o- C~- * iv ! | Mae Me (b) The radical anion of benzophenone is more stable than that of cyclohexanone. Explain. 2 12. (a) “Intramolecular reactions are thermodynamically more favourable than intermolecular reaction” - Comment with proper illustration. 3 (b) What are proton sponges ? Explain with suitable illustation. 2 13. (a) What is meant by primary kinetic isotope effect ? Explain with an example. How this effect can be used in investigation of reaction mechanism? 3 (b) Cyclopropy! methy! carbocation is more stable than ben- zylic carbocation. Explain. 2 Unit- II Answer amy two questions 14. (a) Identify [A], [B] and {C] in the following reaction sequence : a a" cH. SOC of NS wut OH So COO NS 3, Sc cue, Prtidine: 25°C acetone (b) When either enantiomer of 3-chloro-I-butene (R) or (S) is subjected to hydrolysis, the products are optically inactive. Explain. 2 15. (a) The rate of the biomolecular substitution reaction (i) is 20,000 times greater than that of (ii). Explain. (i) CH, S(CH,), + £10° —EIOH_, cH, 081 + (CH3)2S Be 6 ay B® © GO Oi 4(CH.)S6 C.U. Chemistry Hons. Question Papers (Part & !|)-2017 Whi 2 i (b) Which halogen atom will leave easily from the following iS substrate when it undergoes nuclephilic substitution reactio ‘goes nuclephili stl n tion and why 2 i{O)= wie 16. i pi or the product(s) with plausible mechanism when the ig compounds are subjected to acid catalysed hydrolysis : 3 7 :2 H, (b) Predict the product with mechanism : tv (CH,CH,),N CH, CH - CH,CH, BeOS I FIRST PAPER-2017 (Group-B) Full Marks - 50 |CHT -13a] Unit-1 Answer any three questions 1, (a) The molecular speed distribution i E : rae sae peed distribution in 2-dimension is expressed Using the distribution function. show = 4 With the help of the principle of “Equipartition of energy”. m a shov (a ra ‘mi vi kT where ‘m’ is mass of the molecule. a [Given fe-®*' x" db | i n4+1) asi n+l) ) (a+1V/2_ > Q and Pn) = (n-1)!] i. First Paper—2017 7 (b) Calculate the number of binary collisions per cm’ per sec- ond in helium gas at 27°C and | atm. Given that the diameter of He atom =2x10* cm. 2 2. (a) Obtain the expression for Maxwell distribution of kinetic energy from the distribution of molecular speed in 3-D. Point out the differences between the two distributions. 3 _ (b) Calculate the value of (e+ty for'N, gas at 300K, where c is the speed of the gas molecules and © is the average speed. 4 3. (a) Cosider the following equation of state for a gas ‘ pv =RT(1+b/V). Would it be possible to liquify the gas ? Explain your an- swer. 2 (b) If the temperature above which a van der Waals gas cannot be liquefied be 32.3°C and minimum pressure to be applied at that temperature for liquefaction be 48.2 atm, (i) find the diameter of the gas molecule, (ii) Calculate a. 3 4, (a) Define Boyle Temperature (T,) fora real gas. Derive an ¢x- pression for T,, in the case of a van der Waals gas. 2 (b) What is the significance of the reduced equation of state ? Explain whether such an equation is possible for a gas obeying p(V—b)=RT. t 2 5. (a) What is Lennard-Jones 6-12 potential 2 Draw the Lennard- Jones potential against the internuclear distance plot. 3 (b) Two separate bulbs of same yolume are filled with one mole each of an ideal gas A and a real gas B respectively at the same pressure. B is below its Boyle temperature. Which gas has higher temperature ? 2 Unit-1 Answer any 10 questions 6. (a) Identify the extensive ‘and intensive properties from among - the following : i Free Energy, molar enthalpy: heat capacity, temperature. 2 ey ae tae, = 5 Deva 300K and8 C.U. Chemistry Hons. Question Papers (Part-I & !I)-2017 0.5 atm are expanded adiabatically to a final pressure of 0.2 atm against a constant external pressure of 0.1 atm. Calculate the final tempera- ture and AH. ; 3 7. (a) An ideal gas undergoes the following cycle : (i) State 1 + State2, heating at constant volume to raise the temperature from T, to T,. (ii) State2 —» State3, expansion with decrease of tempera- ture from T, to T,, work done by the gas is 1000J while 500J heat enters the system. (iii) State3 + State1, isothermal compression which needs 600J work. Calculate W, Q and AU for each step, explaining the basi of your calculation. 3 (b) A gas expands (i) isothermally from volume V; to V, (ii) adiabatically from volume V, to V, ina leak proof container. Identify the type of system in each case (closed / open / isolated), with proper reasons. 2 8. (a) Show that (GH / OV), =0 for an ideal gas. 2 (b) The heat of formation of HBr(g) from H,(g) and Br,(g) is—9 kcal mol". If 1 mol H, and 99 moles of Br, are exploded in an insulated (adiabatic) bomb Calorimeter, then, neglecting the heat capacity of the bomb itself, calculate the final temperature if the initial tempera- ture was 298K. Assume that all diatomic gases have a constant Cp o 7Tcal K" mol". 3 {CHT - 13b] Unit -1 Answer any fhrree questions 9. (a) A quantity of ideal gas expands (i) isothermally and reversibly at 500K from a volume V, to V,. During the expansion. the gas absorbs 400J of heat from the reservoir in contact with it. Find AS for (a) gas (b) reservoir and (c) the whole system. (ii) If the gas expansion was carried out isothermally but irreversibly for the same volume change from V, to V, absorbing 200) of heat. what would be AQ AC ae ee a z () AG =0,AS > 0,(ji)AG < 0,AS <0. Using this relation, find out the value of ( av 9 First Paper—2017 s in each of which for the system % (b) Give examples of a proces: a.) (2 10. (a) Using Maxwell’s relation show that (F . “Tp b &) for a van der Waals T 3 ; (b) The Helmholtz energy of one mole ofa certain gas is given byA= (=) —RTIn(V-b) +f (T), where a and b are constants and Vv ' {(T) is a function of T only. Setup the expression for pressure of the 2 gas. % 11. (a) Write down the difference bwteen cooling due to 7 be versible adiabatic expansion of a gas and Joule-Thomson cooling. 2 (b) Determine Ss i Scum and ASrotal for the following irre- versible phase transition : H,0 (¢,263K) —>H,0(s, 263K) Given: ‘ ,.-(H,0) = 75.312 JK'mol Eps(H30) = 36-401 JK“'mol Alifeer (at273K) = -6008.2 J mol Miiteee (at263K) = 5619.1 J mol 12. (a) For the reaction, | 3 = o gNale+ 5 Ho) rc NBs (g),10 C.U. Chemistry Hons. Question Papers (Part-| & II)-2017 AG at 298K is—951J mol. Calculate AG at 1000K. if AH for A the reaction is given by, jmerh =-9190-7.12T , 3 mol! (b) Draw temperature versus entropy diagram for Carnot cycle and hence show that area enclosed by the diagram is equal to work done by the system. 2 13. (a) Show that the decrease in Gibbs free energy at a constant pressure and temperature is a measure of the non-mechanical work done by the system. 2 (b) Find the value of j1,; for a gas obeying the equation ev +3) =RT.Comment on the result. « 3 Unit-II Answer any two questions 14. (a) Consider a reaction3A +B -> 2Z. * Ifthe initial rate of consumption of A is 3.36107 mol.dm*. S-!. What are the rate of consumption of B, rate of formation of Z and rate of reaction ? 2 (b) The decomposition of N,O, according to the equation, 2N,05(g)——> 4NO,(g) + 02 (g) is a first-order reaction. After 30 minutes from the start of the decomposition in a closed vessel. the total pressure developed is found to be 284.5mm of Hg and on “complete decomposition” the total pressure is 584.5 mm of Hg. Calculate the rate constant of the reaction. 3 15. (a) The reaction 2NO + O, > 2NO, proceeds through following steps. k, 2NO ine N,O, (fast). AH = x N,0,-+0, 2 2NO, (sl0W) ky where N.O. is the intermediate and (x ) is the equilib- Second Paper —2017 1L rium constant of the fast step. Find the order of the reaction. Com- ment on the sign of x if overall rate constant is found decrease as temperature increases. 3 (b) At 327°C, for the second, order decomposition of NO,, k = 6*10?cm? mols". Calculate the time required for 75% decomposition ofasample of NO, initialy at 380 mm at the same temperature. 2 16. (a) Consider the following Ist order consecutive reaction, slow fast A hg Bernt and hence show that the slowest step is the rate determin- ing step. ft 2 (b) Hydrolysis of ester is simultaneously catalysed both by H* and OH ions. The reaction is first order with respect to each species. 1 ¥ Kon 2 Show that the rate is minimum when. {H"] = E any hae 3 He SECOND PAPER-2017 (Group-A) Full Marks —50 (CHT- 1a) Unit-1 Answer any three questions 1 (a) How do the four quantum numbers signify the state of an electron in a hydrogen atom ? ' 3 ({b) Calculate the shortest wavelngth i in the absorption spec- “trum of deuterium. (Rydberg constant = 109,737 em). 2 £2."(a) Using sketches of 2s and 2p orbits, distinguish between : the radial wavefunction; the radial distribution function and the an- gular wavefunction. 3 ___(b) Write down possible arrangements of electrons in p* nfiguration and identify the arrangement with maximum exchange ergy. 2 3. (a) What do you mean by mass defect in nuclear reactions ? In following disintegration reaction wv. Va12 C.U. Chemistry Hons. Question Papers (Part-1 & Il)-2017 the masses of X, Y, Z are 209.9829, 205.9745 and 4.0026 U respectively. Calculate the amount of energy liberated in MeV. 2 (b) Natural uranium does not indergo spontaneous fission inspite of the presence of Uranium-235 and the availability of neu- trons. Comment. 2 4. (a) How do the nuclei usually adjust the unfavourable n : p ratios ? Give examples. 3 (b) Determine the ground state term for Fe®* ion. 2 5. (a) Write a note on radiocarbon dating for determining the age of coal. Mention also its limitations. 3 (b) What do you mean by isotope effect ? Why is it more promi- nent in case of hydrogen atom than any other atom ? ie Unit-1I Answer any two questions 6. (a) Calculate Pauling’s electronegativity of chlorine from the following data : Bond energies (Kcal mol") : H, (104) ; Cl, (57) ; HC1(102) Pauling’s electronegativity of H is 2.2. 3 (b) The 1* Electron Affinity of Oxygen is negative while the 2 Electron Affinity is positive yet binegative O7 ions are formed. Explain. 2 7. (a) What is Effective Nuclear Charge ? Find the shielding con- stant and Effective Nuclear charge of 3d electron and Is electron in zince (Z = 30). 3 (b) Why do La and Hf have similar chemical properties although they differ much in atomic number and do not belong to the same group of the Periodic Table ? 2 8. (a) Sn (II) is fairly strong reducing agent which is readily oxidised to Sn (IV), but Pb (IV) is a powerful oxidizing agent which is easily reduced to Pb (Il). Explain. 3 (b) Explain why electronegativity of Ge is higher than that of Si and Sn. 2 Second Paper—2017 13 CHT-11b Unit-1 Answer any tree questions 9. (a) BF,, PF, and CIF, are AX, type of molecule, but their structure and bond angles are different. Explain. : 3 (b) Establish the possible grouping of atoms in NO. — 2 10. (a) What do you mean by defects in ionic solids ? Mention their types and two consequences of it. 3 (b) Radius ratio for AgF is 0.86 which indicates cubic structure of CsCl type, but actually it shows octahedral structure. Explain. 2 11. (a) Explain the variation of colour and solubility of halides of silver in the light of Fajan’s rule. ~ 3 (b) Are the bond angles S* (g) using the thermochemical data. Enthalpy of formation MgS (s) : -345 KJ mol"! Enthalpy of sublimation of Mg (s) : 153 KJ mol" IE, +1E,(Mg) : 2184 KI mo Enthalpy of atomization of S, (s) : 559KJ mol"! Lattice energy of MgS (s) :2948KJmol! 3 (b) What are the possible‘arrangements of atoms in hexagonal close packing in metals ? 2 13. (a) BaO is much more soluble in water than MgO but MgSO, is more soluble in water than BaSO,. Explain. Given "yy =65 pm Ty. =140 pm Tyg = 135 pm Sor = 250 Pine 5 4 (b) Magnesium oxide has a higher melting point than Sodium Fluoride. Justify. 2 Unit-ll Answer any @ questions 14. (a) Two unknown acids are being titrated against 0.1 M NaOH - the following pH graphs (a) and (b) are obtained. Suggest with i) n the choice of indicator in each ease.14 C.U. Chemistry Hons. Question Papers (Part-! & Il)-2017 (2) (6) pH (0) —> Vol. of alkali (b) Metals like Calcium, Magnesium, Aluminium exist as car- bonates, oxides etc. in their ore but not as sulphide. Explain. 2 15. (a) What is Hammett acidity function, H,? How can you define a Superacid on its basis ? What happens when SbF, is added to HSO,F ? 3 (b) [Co(CN),1}* and [Co(NH, \, FF are stable While [Co(CN), and [Co(NH,),1]** are unstable complexes! Explain. 16. (a) How will-you explain the following reactions as es, reactions ? (i) NaH + HCI=NaCl+H, (ii) Zn(OH), + 2NaOH = Na, ZnO, + 2H,O. 3 (b) What happens when bismuth nitride and ammonium chlo- ride are allowed to mix in liquid ammonia ? 2 PART-II THIRD PAPER-2017 (Group—A) Full Marks—50 (CHT -22a) Unit-I Answer any three questions (a) Give the appropriate regents to carry out the following trans- eee Explain your answer. - a4 Sequence. Give mechanism of conversion of (B) to (C) 3 Third Paper —2017 15 7\N UH yec —_—_ ee H7 Me HY ‘Me * (b) Write the mechanism of the following reaction : 2 N CH, Me vu MeC = CMe —_} Oo (OHCH)COOH Cy ~°-Nea 1 ae oa 2, : 2. (a) Identify (A) and (B) i int the following two-step reaction and - give mechanism of the first step 3 Me,C.CH = CH; He a) Nee 0) Why is this hydration procedure superior to acid-catalysed hydration of the starting material 2. (b) Arrange the following dienes in order of increasing reactiv- ity in Diels-Alder cycloaddition with tetracyanoethylene. Give suit- able explanation in favour of your choice. i 2 —_ — eee? i ue 3. (a) Write the structures of (A) to (D) in the following reaction MeocH,c1— PPR (4) Phi pp)_PRCHO cy, php =0 |. H.O MeOH +(D) (b) Carry out the following Conversion ; CH,;CHO—-> pj yon ‘OH Nv16 C.U. Chemistry Hons. Question Papers (Part-1 & {I)-2017 4. (a) Carry out the following transformations with appropriate reagents and explain the mechanism in each case OH (b) Predict the product of each of the following reactions: 2 NaCN, HCN qf 5-10°C Ch,-C —~CH=CH, NaCN, HCN 80°C 5. (a) Predict the products (A), (B) and (C) in the following reac- tion sequence : 2 (i) BuLi(ii) BrCH,CO.Et HS(CH,),S ees scmaonno t (C)<—>———___( 1 2, 6-dichloroaniline. (ii) Nitrobenzene ——> p-Nitroaniline (b) Give the products when NaNO, / HCl reacts with the follow- ing compounds separately : A 2 N-- —Methylaniline, N, N-dimethylaniline, benzylamine and benzamide. 11. (a) How can you methylate phenol and ethanol using diazomethane ? Explain with mechanism. 3 (b) How would you employ an enamine compound in the synthesis of 2,6—dimethylcyclo—hexanone from 2—methylcy- clohexanone ? 2 12. (a) What happens when nitrobenzene is aoe under acidic, basic and neutral condition ? 3 (b) Using the Mannich reaction as a guide, suggest a mecha- nism for the following reaction : 2 Cae we RCHO Cat, H 19 Third Paper—2017 ediazonium chloride in weakly ich on boiling with dil. H,SO, 3 ine reacts with benzen rm a compound, wh ;. i ‘ogen. Discuss. benzene to the following oe 13. (a) p-Toluidi acidic medium to forms four compounds excluding nitr f b) Carry out the conversion 0! Pali ooh in single step, with mechanism : , C (A) Unit-HI " Answer any fwo questions dict the products of the following reactions and give the 14. (a) Pre mechanism. o~cl- CH=CH, _A > H,O, / NaOH 2, @ ay : CHO (i) HO Me plain the formation of the product in the following reac- (b) Ex tion with Cc mechanism : : Xe “mCPBA, oF CH.Cl, “CHCA 3 NO, ‘I ON So 15. (a) Explain the fe following reaction : ib PhNMe, / H? i 1 y 2 Ea ON OS od20 CU. Chemistry Hons. Question Papers (Pant & M!)-2047 * NMe; not formed 9 correct stereochemistry and give the mechanism 2 Ph O 2” ae z : HC HG AG). CHch A (ii) EtOH 16. (a) Predict the major products of the following reaction and xplain the plausible mechanism : ‘ OMe MeO er OB AO (b) Com Product : plete the reaction indicating the Stereochemistry of the 1. PCI, 2uERO aby THIRD PAPER-2017 (Group—B) Full Marks ~50 (CHT-23a) Unit-I Answer any three questions ou )) {6G 1. (@) Show that 4=|——| = an 3 )eeayen, "AT Pnjen, (b) In 0.10 (M) solution of sodium acetate, calculate K, (hy- drolysis constant) and PH of the solution at 298 K, Given : At298 K, K,= 10 * 10", K, (acetic acid) = 1.8x10-5 i 2 2. (a) Derive the expression of fugacity coefficient of a gas obey- ing the equation P(V—b) = RT. 3 (b) For N,O, (g) ==2NO, @). by what factor would the value of K, change if the standard state were taken to be 0.5 bar instead of 1.0 bar? i 2 3. (a) If €. is the equilibrium value of the advancement €ofa : =| AH Feaction, show that | =¢ | =—1. ction, sho [S Tae &G [Where AY = enthalpy of the reaction and Gi= | a bs equilibrium 3 (b) The solubility of KHTa (Potassium hydrogen tartrate) in Water increases when NaNO, is added to it, Explain. ' 2 4. (a) For the dissociation N,O, (g) =2NO, (g). show that K 3 ‘eal ee Pe ()K=K_p, (ii) Seq (AS ts}22 C.U. Chemistry Hons. Question Papers (Part-I & Il)-2017 Where ¢¢q is extent of reactign at equilibrium. (b) Calculate the mean ionic activity coefficient of the electro- lyte in an aqueous solution of 0.01 M K, [Fe(CN),] at 298 K. [Given : Debye- Hiickel constant for water at 298 K = 0.509] 2 5. (a) Consider two important relations : AG? =-RT InK, (van’t Hoff isotherm) (Gibbs-Helmholtz relation) ae AH a (ac? /7) = = Combine these two relations. Justify that the resulting equation is in accord with Le Chatelier’s principle. 2. (b) For a particular gas phase reaction K,, values were mea- 1 sured at different temperatures (7). A plot of In K, vs. T gives a straight line with slope of 10°K. Mention the condition that supports such a plot. Calculate A,H° . 5 Unit-1I : Answer amy two questions 6. (a) Show that the excess pressure inside a spherical bubble is 2 given by Py — Ff a where P, and F, are the pressure inside and 2 outside the bubble respectively, and r is the radious of the bubble. r 3 (b) What is Reynold’s number ? State all the terms involved in the expression for Reynold’s number. 2 7. (a) Find the inside diameter of a glass capillary in wifich water shows a capillary rise of 88 mm at25°C. Given (at 25°C, latm): ¥ (water) =72.0 dyne /cm, density of water is 0.997 g/cm’. 2 wie 2 ny Third Paper —2017 (b) Graphically represent the variation of surface tension (7 ) a liquid with temperature (7). i ie ae Explain the significance of the point on the graph at critical 1 temperature. 25 8. (a)Atacertain temperature, for pure CH,I,, 7=51 mN/m and for water, 7 =73 mN/m; and their interfacial tension is 46 mN/m. Calculate ~ the work of adhesion between CHI, and water. 2 (b) Explain the temperature dependence of viscosity coefficient of liquids. How can the activation energy of viscous flow be caleu- lated graphcally ? é 3 CHT 23b Unit—1 Answer any three questions 9. (a) What is Compton wavelength ? (ii) State the significance of the Compton Effect. 3 (b) Show that a small change in the speed of a particle Av, ; Av} A causes a change in its de Broglie wavelength | AA neh ; where 0. Yo and Ag are its initial speed and de Broglie wavelength respec- a 2 tively. - ¥ e at e d d se 10. (a) Are the two operators, md ae Hermitian ? Assume that —co ggx = +0.27V and b (=) =-3.2*104 VK ; F=96500 coulomb/equivalent. rs Find the values of AH’ and AS” of the reaction. 3 (b) Find the number of moles of NH,CI required to prevent Mg(OR), from precipitating in a litre of solution which contains 0.02 mole of NH, and 0.001 mole of Mg. . [Given K, (NH,)= 10°, K,, of Mg (OH), =10"]. n2. FOURTH PAPER~2017 (Group-A) Full Marks —50 (CHT-21a) Unit-1 Answer any three questions 1. (a) Solubility trend of fluorides of alkali metals in water are (CsF>RbF>KF>NaF>LiF but this trend is reverse for iodides. Explain. 3 (b) Explain why Pb(IV) compounds are powerful oxidising ; i: agents. a 2. (a) Compare perbromic and periodic acids with respect to (i) Formula (ii) Acidity Git) Relative stability. 3 (b) Why AsCI, is unstable in comparison to PCI, and SbCl, ? oy26 C.U. Chemistry Hons. Question Papers (Part-I & II)-2017 3. (a) Predict and explain the order of the ‘tendency of polymer- ization’ of the following oxyanions : i S07, CIO;, POF, SiO}. 3 (b) Xenate anions slowly decompose in basic solution: Give a balanced equation to justify the statement. 2 4, (a) O-O bond in O,F, is much shorter than that in H,O, whereas O-F bond length in O,F, is longer compared to that in OF,,. Justify the statement. 3 (b) Compare the elemental form of nitrogen with that of phos- phorus, giving reasons. 2 5. (a) Solid state structure of PCI, differs significantly from its gas phase pattern. Give reasons thereof. 3 (b) Explain : SF, is a stable compound but SH, and SF, are non- existent. i 2 Unit-2 Answer any fwo questions 6. (a) Draw the MO diagram of NO and explain the magnetic behaviour of the following : 3 NO',NO,NO” (b) Write IUPAC nomenclature of : OH @ [ONH,),Co (44> Coen), J" (ii) [Cr(NH,),CO,],[CuCh,] 7. (a) Draw the three possible isomers of the complex CO(NH,),(CO,)CI and mention the type of isomers. 3 (b) Sodium bicarbonate is less soluble in water than sodium carbonate — Explain. 2 8. (a) Metal chelates are more stable than non-chelated complexes. Comment. 3 (b) Explain the effect of temperature on the variation of con- duction of metals and semiconductors. 2 Fourth Paper— 2017 CHF21b Unit-1 : tions Answer any three question ; ol features of diborane. Explain the ict the struct " eri Ease as a Lewis acid with reference to ammonia and reac : gai : (b) Discuss the bonding involved in (SN), where x = 4. 2 de is commonly called as inorganic graphite. idering the structural aspects. 3 i ise the statement considering t c s Ratt wat happens when an aqueous solution of chromium sulfate is slowly heated with potassium peroxodisulfate in H,SO, 10. (a) Boron nitri 2 ium i f Ag’ ion ? "a ey aia are ‘iibeased phospates 2 Write down the structure of a polyphospahate and cyclic metaphosphate. 3 (b) Draw the structure of borax and mention its importance as : laboratory reagent. - t f a Eo cnapie the reactions and balance in each case : (i) XeF, + SbF, > (ii) XeF, +KI > (ii) XeF, + SiO, > i (b) Cyanogen is a pseudohalogen — Justify. 2 13. (a) Comment on the complexation of N; and SCN with metal 3 ions. i (b) Show a schematic presentatoin of separation of noble gas: from liquid air. es 2 Unit-2 Answer any two questions : : 14. (a) From the following Latimer diagram (in acid medium) : 5 > 1s1V. 2+ - _0.56V sy 226V 0.95V Mn** Mn’ MnO, = >Mnof —>Mn0, ———> —, 3 Predict : (i) Whether MnO, or MnOz is the better oxidant if ‘the reduction product is \n?*- ‘ ae (ii) The stability of Mn* with respect to disproportination.28 C.U. Chemistry Hons. Question Papers (Part-I & I1}-2017 (b) Sodium carbonate cannot be used instead of ammonium carbonate to precipitate the cations of GrIV in qualitative analysis— _ Justify. 2 15. (a) The formation constant for [Co(NH;)¢]}°* is 5*10% and for [Co(NH3),F* is 1x10*. Show that an aqueous solution of [Co(NH;), p* in IM NH, does not oxidise water. Given: EQ, c+ = +1-84V and Ely, 3,9 = +1-23V. 8 (b) Ammonia gas is evolved when sodium nitrite is boiled with aluminium and caustic potash. Write the balanced equation by ion- electron method. 2 16. (a) Hg* reduces Fe* in presence of SCN’ though Hg?* /Hg3* couple (E° = 0.92V) is more oxidizing than Fe**/Fe* couple (E°=0.77V) — Explain. aided (b) Predict whether the following reactions will go to comple- tion : : 2 4 2 . Zn ig) + CU (aq) => ZN(aq) + Cis) [ES 2j¢y-= 0,337. and E9, 2), = -0.763V] wyCu‘ CALCUTTA UNIVERSITY EMISTRY (HONS.) QUESTION PAPERS (PART - IID) — 2017 FIFTH PAPER — 2017 243) Full Marks — 100 Ta (CHT ~ 31a) 3 ofa Unit —1 Answer any three questions 1. (2) Draw all the possible isomers of the complex {Co(NO,), H, ),] * 3 _ (6) Explain with Proper diagram the source of colour for pale violet 1m ofrCl,.6H,O . 2 2 (a) The electronic spectrum of [TicH,0), ]” shows a broad band ith a peak at 20,000 cm” and 17,400 cm. Assign the ligand field a for both the peak and the shoulder. Find the value of 10 Dq of ie Ti ion, for the H,O ligand. 2 3+] (b) Discuss the d orbital splitting in complex ion [Ni(CN), }° and [ sity. 2 3. (a) Both in tetrahedral complexes and high spin octahedral Yomplexes, Co(II) has three unpaired electrons, Yet the tetrahedral omplexes have lower magnetic moments than the high spin octahedral omiplexes and both groups have moments significantly higher than the redicted spin only values, Explain. 3 (b) Using CFSE, indicate whether Co,O, isanormal or an inverted "Spinel. 2 4. (a) The logarithm of Stability constant values of Cu(en)* , Cu(NH,);*, Ag(en)”* and Ag(NH, ):*. complexes are 10.7, 7.8, 4.7 and 2 respectively. Rationalise the above data. (b) Cite two examples to illustrate the application of Trans effect in 0-ordination complexes. 2 5. (a) Both copper (d’) acetate monohydrate and chromium (d*) acetate onohydrate have similar structure; the former is paramagnetic with lower Lt, Value but the latter is completely diamagnetic at room temperature. ow will you explain the above facts? 3 .U. CHEMISTRY (H) (2017)-l1/ 42 P: Part—III)-2017 C.U. Chemistry Hons. Question Papers (Part: )-20 (b) What do i you mean by labile complexes? Whi do generally behave as labile Ee oe eres a Unit -0 ’ nswer any two questio 6. (a) What are the main di ( main differences in tl i behaviours among the elements of 4f and sf a CT ? 3 (b) How is K,C rere 2Cr,O, prepared? Discuss its use as an analytical 2 7. (a) Explain briefly the princi ee ly the principle of separation of lanthanides by ion 3 (b) Comment on th ¢ statement : i i tothat of W than that of Cr. nt: The chemistry of Mo is more similar 2 8. (a) Explain the red ili ; lox stabiliti H to + 2 and + 3 oxidation states, a eee 6 : (b) Compare the chemistry of Zn and Cd with that of Hg. : (CHT — 31b) c Unit -I Answer any three questions . (a) Do you ex) ly e ethylene molecule in Zeise’s 9. pect any rotation of th y! salt, without hampering the stability of the complex? Explain your answer. (b) Olefin polymerisati 3 i Dries tion by Zi - : olefin insertion into the metal alk] eee ORE ‘ i 2 10. (a) Explain the carb i the following eat - ee ne ] ¢ [cr(CO),] [Mo(Co),] © [W(CO),] [¥(CO.cm"] 2000 1984 1960 3 (b) What is Oxidati iti ‘i HG ive Addition Reaction? Illustrate with a suitable 11. (a) How will i AL. ( you chemically show thi A at the twi i gs ‘ aii freely rotate around the a ae )) What are fluxienal molecules? Give one « ‘aaae i 2 12. (a) Discuss the mechanisti 7 h : : ne eee anistic steps for the hydrogenation of olefins 3 of 0.01 (M) ceric ion so} ~ 0.01(M) Fe® solution given E, (Fe* /Fe*)= 0.77V, E, Fifth Paper — 2017 (b) Show the mode of binding of NO in transition metal complexes. a 13, (a) Why cannot ferrocene undergo nitration reaction similar to that of benzene? How can nitroferrocene be prepared? a (b) [Fe(tH,0),NO] shows [1.q = 3-92 - Explain. 2 Unit -Il Answer any two questions 14. (a) Why is CH,Hg* more toxic than Hg”? : 3 (b) Name the metal ion present at the active site of carbonic anhydrase and explain its biological function. 2 15. (a) Explain the mechanism of metal ion transport across biomembranes, with particular reference to the functioning of Na‘ /K° uM] a of Mg” ion in biological system. 2 p. (b) Explain the role the biofunction of cytochrome C highlighting 3 16. (a) Discuss briefly the active site structure. (b) Name two platinum complexe: treatment of human cancer. (CHT - 3c) Unit -1 Answer any three questions 17. (a) Calculate the potential ofa cell after addition of 5 ml.and 50 ml Jution with SCE and Pt electrode to 25 mL. (Ce*/ gery 3 s approved clinically for the 2 1.61V, E(SCE) = 0.285V - (b) Give the steps of spectrophotometric estimation of total ion in 2 a water sample. 18. (a) Drawa sketch to represent schematically the set up of the atomic absorption spectroscopy: State one advantage of atomic absorption spectroscopy over atomic emission spectroscopy: 3 (b) Discuss any two factors that affect the selectivity ofion exchange 2 resins. 19. (a) The ideal chromatographic process © an be assessed in terms of column efficiency and resolution. Comment. 3 aNC.U. Chemistry Hons. Question Papers (Part-III1)-2017 {b) A compound having molecular weigh ay \ it 282 absorbed radiation at 455 nm ina | cm cell at a concentration of 8 ay L Wis * a sewn of the compound? 2 . (a) If the emf of the following cell is 0 E the unknown solution (C,,) at 25°C. Ine Sears Pi Pdi N, tH,)| HC], Nf ggg | HCL, C,, / PtCH,) (b) Outline the principle of the estimati e estimation of ium i =. n atomic absorption spectroscopy. ang: om - (a) What do you understand by i : u y the exchange capacity of an ion- exchange resin? Mention one practical application of ion-exchange tb (b) State two different types of i i : (), { interference in the analysis with atomic absorption spectroscopy. How are they minimised or eliminated? 3 3 Unit -II c Answer any fwo questions . (a) What do you mean by standard deviati i ) ¢ leviation? Give a mathematical ee for it. Compute the standard deviation value for the following 's from the analysis of a sample of iron ore. Iron content (%) : 7.08, 7.21, 7.12, 7.09, 7.16, 7.14, 7.07, 7.14, 7.18, 7.11. 3 (b) How will you detect and estimate NH,’ ion in a water sample? 23. (a) What do yor i c dae you mean by TDS in a water sample? How will you (b) Distinguish between accuracy and precision. 3 24. Q eed the principle of estimation of H,S in an air sample. 3 Se 4 i mg of Ag one in the course of analysis of the ment. 1 percentage of relative i i weight of Ag in the sample is 400 mg. - oe ae (CHT -31d) Unit +I Answer any three questions 25. (a) Outline the sch ji : : aeidiiesia cheme of analysis of basic slag, with the appropriate B (b) Explain the role of a ion indicator in cc Pa metal ion indicator in complexometric 2 Fifth Paper — 2017 26. (a) A0.7120 ¢ specimen of jron ore is brought into solution and all iron content is reduced to Fe(II). The reduced solution in 2N acid, requires 39.20 mL of 0.02 M KMnO, solution for titration of Fe(II). Calculate the percentage of iron in the ore. a (b) Indicate one use of oxine in the gravimetric estimation of an inorganic cation. 2 27. (a) 0.15 gm of an ore containing MnO, was treated with excess HCI. The chlorine formed was distilled off and absorbed ip KI solution. Titration of the liberated iodine requires 40.5 mi. of 0.0492 N sodium thiosulphate. Calculate the percentage of MnO, in the ore. 3 (b) How does an adsorption indicator work? State the conditions for the choice of an adsorption indicator using a suitable example. 2 28. (a) What are co-precipitation and post-precipitation? How can those be avoided during gravimetric analysis? 3 (b) State any two advantages of organic precipitating agents over 2 inorganic precipitating agents. 29. (a) Discuss the principle of complexometric estimation of a mixture of Fe** and Al** in an aqueous solution. 8 (b) Why is Mg-EDTA used in the complexometric estimation of Ca?* ion in aqueous solution? ‘ 2 Unit - II Answer any two questions 30. (a) Arrange and explain the solubility trends of MSO, and M(OH), salts [ M = alkaline earth metals] in water. 3 (b) Explain why sodium carbonate cannot be used instead of ammonium carbonate to precipitate Ca’* ion in presence of Mg**ion. 2 31. (a) Select the least and the most basic anion out of F ~, CH,, ry C*.'Give reasons. i. (b) A sample of AgCl dissolves in conc. HCI but precipitates on dilution. Explain. 2 32. (a) Write the Born Equation. Why solubilities calculated from it do not agree appreciably with those found experimentally? 3 (b) How can acidity of cations be related to their respective charge - and size?6 C.U. Chemistry Hons. Question Papers (Part—III)—2017 SIXTH PAPER — 2017 (Group — A) Full Marks — 75 CHT - 32a Unit -1 Answer any three questions 1. (a) Acetolysis of both cis- and trai 2 ins-tosylate sh i the same trans diacetate. Explain enero tye “ OTs Cees Lor" OAc OAc (b) trans-1,3-Di-tert-butyl i t f yleyclohexane prefers twist b conformatio} i its cis-i i i ic. a n and readily passes to its cis-isomer on heating with Ce 2. (a) Which side reaction prevails with i rf V acetoacetic ester but not with te base catalysed alkylation? Discuss the influence of solvent and size of alkyl group on the ratio of C— vs. 0— alkylation, 8 (b) Write down the probable mechanism of the following reaction: 2 ° cl ‘ sont + Be 1. NaOEt ———> 0 2. NaCl/DMSO : 3. OH/H,O ‘ 3. (a) The cis-I,2-dimethyleyclohexane is less stable than its trans isomer, but cis-1,3-dimethylcyclohexane is more stable than its trans isomer. Draw the most stable conformations of both and explain. 3 (b) Suggest a possible mechanism for the followin ig transformation: 2 ° Me Me. N COOEt COE ee: 4. (a) Both cis- and trans- 1,2-dibromocyclohexanes ‘give the same product when heated with iodide ion. Identify the product and explain the reactions. . g Sixth Paper — 2017 7 (b) Justiiy the fact that although iodine is larger than chlorine, the conformational energies of chlorocyclohexane and iodocyclohexane are the same. 2 5. (a) Explain the fact that trans-4-tert-butylcyclohexyltosylate undergoes bimolecular elimination with thiophenate, but not with much stronger base ethoxide. 3 (b) Write the preferred conformation of 4-hydroxy-N-methypiperi- dine with explanation. PA Unit - Il Answer any two questions 6. (a) An organic compound with molecular formula C,,H,,0, gives positive iodoform test. Its UV, IR and 'H NMR data are given below ; deduce the structure of the molecule. IR: 3050, 2950,1730 cm”. 'H NMR: 6 1.3 (d, 6H). 5.2 (m, 1H), 7.2 (m, 3H), 8.0 (m, 2H). 3 (b) Distinguish vinyl acetate and methyl acrylate by IR ie spectroscopy. 7. (a) How would you distinguish between the members of the following pairs? : 3 @ Ce & >: (by IR spectroscopy) (ii) o-Fluoro phenol and p-fluoro phenol (by 'd NMR Spectroscopy) (b) Why the C=C str. of acetylene is IR inactive? 2 8. (a) The o,f unsaturated ketone, mesityl oxide shows A,,, 230 nm (¢=12,600) and 329 nm (€=41) in hexane and A,,. 243. nm - (€=10,000) and 305 nm (¢ = 60) in water. Explain. 3 (b) Define the term chemical shift. What difference in chemical ' shift values are expected for the protons of CH,F, CH,Cl and CH,Br? Explain. m an8 C.U. Chemistry Hons. Question Papers (Part-III)-2017 CHT -32b Unit -1 Answer any three questions (a) S tl 9. (a) Show the retrosynthetic analysis of the following compound (b) Outline the i + Talent synthesis of the following compound from diethyl 2 9 10. (a) How will you carry out the following transformations? 3 9 So CO,Et AL on 5 a tk : oO (b) Predict the product with plausible mechanism Nv Ph OH H,SO, OMY Canara Ph ll. i nb < Rovh cy — that “all stereospecific reactions are c all stereoselective reacti i stereospecific”. Give proper example eet: (b) Show the product in the fc flaws i la oman ¢ following reaction and explain the cl ° NaOEt ere Sixth Paper — 2017 9 12. (a) Alcoholic functionalities are often protected by making its t- butylether as ROH + ROCMe,, What advantage does this t-butyl group provide? Mention the protection and deprotection techniques. 2 (b) Using protection and deprotection techniques, outline the following transformations : 3 OH OH OH OH Ph Ph jet e ° Dee Br 13. (a) Illustrate the use of acyloin reaction for the synthesis of large rings. Discuss the role of trimethylsilylchloride which can be used to improve the yield. 3 (b) Describe the synthesis of the following compounds with proper 2 retrosynthetic analysis (any one) : COOEt ie QO @ (i) a es ry ‘OH Unit - 1 Answer any two questions 14. (a) Deduce the absolute structure of the L-aldopentose from the following observations : —— When oxidized with HNO, an optically active compound is produced. —_ On Ruff’s degradation a tetrose sugar is produced which on treatment with NaBH, gives an optically inactive compound. 3 (b) Give the mechanism of acid catalyzed conversion of aldopentose into furfural. 2 15. (a) Clearly represent the most stable conformation of the B- pyranose form of the following sugars and justify : 3 (i) L-glucose (ii) D-fructose. (b) Convert D-arabinose to D-Glucose. 2 16. (a) Bromine water oxidation of o -D-glucose is 400 times slower than that of B -D-glucose. Explain with mechanism. 310 C.U. Chemi: emistry Hons. Question Papers (Part-III)—-2017 __(b) Explain why D-fr ie een hee, y D-fructose reduces Fehling’s solution although it CHT-32¢ 2 Unit-I 17. (a) Sais Nay ae b any three questions substitution but i is not only reactive towai a Aiport Rs as seen to a reactive ae bit ate ne account for the reactivi : Bie (b) Predict the product with possible Con er ; 2 co CHCI/NaOH 5 aeOUeOr fri.) OCH, 18. 8. (a) Account for the following observations: H H H What strate; a ; wi i heuer gy would you take to get 3-nitro pyrrole as the majo or (b) The followi ing deox: ana 3 re ygenat ; arrangement. Suggest a reasonable eae eccemenniet with ir it. 9 DS Ph LPOEL), Ph No, Me a | N H Me ( 19. (a) Predict the products formed from the reaction of maleic anhydride with (i es ae (i) furan (ii) N-methylpyrrole. Give reasons for your s (b) Write the pro @F & C3 N reaction the pH of the me (h) Draw th case of mutarotation (b) How would you conv Sixth Paper — 2017 PhMgBr Pa eee \ NaNHJliq.NH; 20. (a) Outline Bardhan Sengupta (b) 1,2-bond of naphthalene has than 2,3-bond. Explain. 21. (a) How one can starting materials? Write mec! (b) Write the product wil synthesis of phenanthrene. get pyrrole ring by takin hanistic details. ith plausible mec duct with mechanism : 5 greater double bond character 2 g, EAA as one of the s hanism of the following 4. Ethanolic KOH,4 2 9,10- henanthraquinone q a 2.4? Unit - 0 Answer any two questions 22. (a) Specific rotation of optically dium is changed. Explain the or any other process. ert glycil Erlenmeyer azalactone synthesis? 23. (a) Write thi gly-ala. e steps for the solvent phase synthesis 0 (b) Predict the product with m with acetic anhydride in presence of 24. (a) How is N-terminal Why is it more advantageous e structure of thym amino acid changes when active fact stating whether itisa 3 ne > phenylalanine using 2 fa di-peptide 3 echanism when leucine is heated 2 pyridine. idine monophosphate. amino acid determined by Edman’s method? than Sanger’s method? 3 2SEVENTH PAPER - 2017 (Group ~ A) Full Marks — 75 (CHT — 33a) Unit +1 Answer any three questions l. (a) The density of Lithium i Inetal is 0.53 gem and the s i of the 100 Planes of the metal is 350 pm. Determine whether sa is fee or bee, [At. Wt. of Li= 6.941] 3 (b) Temperature Variation of izati ol; i non-polar nature of a substance. ce ee 00 is ay a 3 ee and fy, amount adsorbed js expressed in milli-mole of dye/ cot ic i ea 15 ps yf activated charcoal is shaken with 150ml R ion of the i libri concentration of the solution? He aE Ya) ks, vee 5. (a) Define with an exam iLic i ane, witha ple, a vophilic colloid. How ma such a colloid help in Stabilizing a lyophobic Colloid like a gold sol ? Explain what ik mean by the term “gold number’ 3 ) What is Tyndall effect? Wh: 7 i f f ? at type of inf ti gather from the quantitative data of such deat on a "3 Le eee Seventh Paper — 2017 13 Unit — IL Answer any two questions 6. (a) Verify that the wave function A exp (— Bx?/2) is an eigenfunction of the Simple Harmonic Oscillator (in one dimension) Hamiltonian. Here B=2nV/mk/h (terms have their usual significance). Find the expression for the eigenvalue. 3 (b) From the eigenvalue obtained above, make an estimate of the Positions of the Classical Turning Points x, and x, i.e., values of x after which the motion reverses its direction. Use proper arguements. z 7. (a) The 1s wavefunction for the hydrogen is ‘Y = (xa,') "se where a, is the Bohr radius. Calculate the probability of finding the electron within a distance a, from the nucleus. 8 Given: [x'e “dx = n/b™ (n> —1) lo (b) For the 1s wavefunction find , the average distance of the electron from the nucleus. 2 8. (a) The 2s wavefunction for the hydrogen atom is Y, = NO 1/ ‘a,je where N is a constant, r is the distance from the nucleus and a, is the Bohr radius. Find the distances from the nucleus, in terms of a,, at which the radial probability. density shows maxima. 3 i (b) Justify the existence of a non-zero zero point energy in case of _ a quantum harmonic oscillator in the light of Heisenberg Uncertainty _ Principle. 2 * (CHT ~33p) Unit -I Answer any three questions m9. (a) Draw the phase diagram (‘T’ versus mole % of B) ofa system Consisting of solids A and B forming a stable compound A, B with _ Congruent melting point. Show the different phases present in the different Tegions of the diagram. State the degrees of freedom at eutectic point. {Given: m.p. of A,B> mp. of A> m.p. of B] 3 (b) Ammonium chloride decomposes on heating to give ammonia and HCI gas. How many components and phases are present if the salt _ Js heated in an otherwise empty container? 2 10. (a) For CCl, K,= 5.03 Kkg/mol and K,=31.8 Kkg/mol. If 3.0. gm Of a substance in 100 gm of CCl, raises the boiling point by 0.6K, Calculate the depression of freezing point, the relative lowering of vapour Pressure and the molar mass of the substance (given density of CCL =1.59 /ec and molar mass is 153.823 gm/mole). : 314 Gy Chemistry Hons, Question Papers (Part-II1)-2017 (b) Show with the help of the phase rule that at a given pressure, the critical solution temperature (CST) is a non-variant point, 2 11. (a) Find the expressions for AG. and AS, for an ideal binary solution, 3 (b) Explain Konowaloff’s rule. 2 12. (a) Draw the versus T diagram for a Pure substance (A) in its three states of matter. Draw the plot of 1 — T for the solution of a substance B in A to demonstrate that the solution has a depressed freezing point but an elevated boiling point. (b) A mixture of quinoline and water boils at 98.9°C under a Pressure of 740 mm Hg. The distillate contains 78g of quinoline and approximations you use. 3 (b) Justify or criticize the statement — “A binary solution may exhibit an elevation of freezing point”. 2 Unit —TI Answer any two questions 14. (a) The Boltzmann distribution may be represented by expressing the number of molecules (N,) in the level €, (under isothermal conditions) as N\=A exp(-be, ) where A and b are constants. Answer the following questions taking b = Ifk,T : (a) Show that N,, < N, for any finite temperature, with e, [Co(NH,),OH]” + Br- Was studied in aqueous solution of (i) 0.1(N) KCl and (ii) 0.01 (N) KCL. State with reasons whether the rate constant of the reaction in case (ii) would be greater, lesser or equal to that in case (i). 3 (b) Explain whether or not the overall rate of a chemical reaction which is initiated by absorption of light will be guided by Arrhenius equation. 2 21. (a) Outline the fundamental assumptions of Transition State theory, i 3 (b) State in which important ways it differs from the Collision theory. 2 Unit — 11 ; Answer any two questions 22. (a) The rotational Spectrum of HF has lines which are 41.9 cm”! apart. Calculate the bond length in HF. [Given: At. Wt. of H= 1, F = 19, N, = 6.022 x 103 mol]. What will be the Spacing between lines if DF was investigated? [D = 2] (Assume the bond length to remain unaltered upon isotopic substitution.) 3 (b) Justify or criticize: “The nature of Raman spectrum of a~ substance depends on both the nature of molecules and the wavelength of incident radiation”, 2 23. (a) The hydrogen chloride molecule when subjected to IR radiation shows absorption at 2885 em" and 5679 cm", fundamental and first and the position of the first “hot band’. 3 (b) How many times does a molecule of 'H®C1 rotate per second in the J = 1 rotational level? (Given B = 10.6 cm). Comment: “The speed of rotation of a?H°°C1 molecule will be the same as that of '45C1 molecule”, ere 24. (a) A linear molecule has the formula AB,. Discuss how would you ascertain whether the molecule has the structure BAB or ABB, using its Raman and IR spectra together. 3 (b) If the J=2 to J=3 rotational transition for a heteronuclear diatomic molecule occurs at 4=20 mm find the wave number for transition from J = 5 to} = 6 level in the same molecule. 2 CITY Go s