©®20000099000 @e9 eecoaoeoocegoooe oo ‘Chapterwise Previous Years' SOLVED PAPERS (2014-2000) GATE Chemistry Dr Sanjay Saxena + Preeti Gupta ARIHANT PUBLICATIONS (INDIA) LIMITEDARIHANT PUBLICATIONS (INDIA) LIMITED All rights reserved % © Publisher ‘No part of this publication may be re-produced, stored in a retrieval system or distributed in any form orby any means, electronic, mechanical, photocopying, recording, scanning, Web or otiverwise without the written permission of the publisher. Arihant has obtained all the information in this book from the sources believed wo be reliable and tue. 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The score is used for admissions to post-graduate engineering programmes (e.g., M.E., M.Tech, direct Ph.D.) in Indian higher education institutes with financial assistance provided by MHRD and other Government agencies. The score may also used by Public sector units for employment screening purposes. Most of the PSUs are looking for GATE qualified. IOC{. was the first PSU which successfully tested out the system and was allowed that GATE qualified seekers only can apply and their percentile was also had defined for ranking in recruitment process, two years later it has been followed by NTPC, BHEL, BEL & Powergrid. Usually these companies release their recruitment notifications right after GATE notification, indicating that candidates have to take GATE to be considered for a job in their organisations. So making a great score in GATE is very considerable for availing all these opportunities. Keeping the above point of view and after exhaustive research, | have come up with the Solved Papers of Chemistry for the aspirants who are preparing for GATE Exam which contains previous years’ (2014-2000) GATE Solved Papers with their authentic solutions to help you getting a good score. The chapter wise solved papers in this book will help the students to find solutions to their problems and get through the exam without any difficulty. This integrated package of solved papers has been designed to help the students to get away with their initial qualms about the GATE, to know about the GATE Exam pattern and the level ofthe Exam as difficult and moderate , and to scrutinized the GATE papers and the change in trend as well. After going through this solved paper aspirants can climb the ladder of success and fulfill their dreams. We are thankful to Arihant Publications (India) Limited for giving us this opportunity to make such book which will help you to get 100% success in GATE exam, Valuable suggestions are always welcome for further improvement. AuthorsInside the Pages... GATE (Graduate Aptitude Test in Engineeting) Recent Changes in GATE Strategies to Crack GATE 9 Tips for a Successful Attempt GATE 2016 Syllabus + Solved Paper 2014 (Online Set) + Solved Paper 2013 + Solved Paper 2012 1. Atomic Structure 2. Chemical Bonding and Molecular Structure 3. s-Bilock and p-Block Elements 4, Transition Elements 5, Chemical and lonic Equilibrium 6. Electrochemistry 7. Chemical Kinetics 8. Chemical Thermodynamics 9. Basics of Organic Reaction Mechanism 10. General Aptitude « Practice Set-1 « Practice Set-2 « PracticeSet-3 415 5 1-16 1-9 10-19 20-26 27-43 44-48 49-53 54-62 63-68 69-120 121-134 137-145, 146-150 151-156 9 ee © gSSoo ® GATE Graduate Aptitude Test in Engineering Graduate Aptitude Test in Engineerin an all India level examination, conducted and controlled by the Indian Institute of Science in cooperation with seven Indian Institutes of Technology on behaif ofthe National Coordination Board ~ GATE, Department of Higher Education, Ministry of Human Resource Development (MHRD), and Government of India. The GATE committee which consists of representatives from the governing institutes is the sole authority for conducting the examination and declaring the results. GATE Eligibility Criteria ‘The following categories of candidates are eligible to appear in GATE * Candidates with Bachelor Degree in Engineeting/Technology/Arcitecture (4 years ater 10#2) andthose whore nthe nal ofsuch programme. * Candidates with Master Degree in any branch of Science/Mathematics/Statisties/ Computer Applications orits equivalent and those who are in the finalyearof such programme. 2800000602 * Candidates in the second/third/higher year of the Fouryear Integrated Master Degree Programme (Post &.Sc) in Engineering/Technology, or 4th/Sth year of Five-year Integrated Master Degree Programme and Dual Degree Programme in Engineering/ Technology * Candidates with qualifications obtained through examinations conducted by professional societies recognized by UPSC/AICTE (e.g. AMIE by IE () AMICE () by the Institute of Civil Engineers (India) -ICE ()) as equivalentto B.E./B. Tech. The students who hiave completed his/ her bachelor degree in Engineering (4 years after 10+2) or equivalent of such professional coursesare also eligible Zones and Institutes for GATE ‘The GATE is conducted and controlled through eight zones which ae a follow Zone lISC, Bangalore Zone® IIT, Bombay Foae 8 NF, Death one INT, Guwahati one 5 \iT, Kanpur Tone 6 MT, Kharagpur Examination Pattern ‘The GATE consists of a single paper of 3 hours duration, which contains 65 questions carrying maximum of 100 marks. The ‘question paper is divided into three sections. First section consists of 25 questions of ONE MARK each. Second section consists of 30 questions (26 to 55) of TWO. MARKS each, Third section consists of 10 questions (56 to 65) of ONE MARK (56t0. 60) and TWO MARKS (61 to 65) each. e & S e 6 © © eS Multiple Choice and Numerical Answer Type Questions The question paper consist of multiple choice and numerical Zone7 IT, Madras answer type questions. In multiple choice type question, each Zone 8 IIT, Roorkee question has four choices forthe answer. Innumericalanswertyoe {GATE 2014 exam was conducted by questions, there will be no responses 0 mark at all. To enter a {ir Kharagpue number as your answer, use the virtual numerical keyboard displayedon the monitor.Common Data and Linked Answer Questions. The 2 marks questions also include two pairs of common data questions and two pairs of linked answer questions. ‘The answer to the second question of the linked answer questions depends on the answer to the first question of the pair if the first question in the linked pair is wrongly answered or is not attempted, then the answer to the second question in the pair will nt be evaluated. Although, there were ne any question of common data and linked answer in GATE 2014. Negative Marking in GATE Exam Incorrect answer cary negative marks i.e, 0.33 for one mark questions and 0.66 for twomarks questions. However, in the case ofthelinked answer question pair, there willbenegative marks only for wrong answerto the fist question and no negative marks for wrong answer tothe second question. There s no negative marking for questions of numerical answertype, Answering a Question in Online Test Procedure for answering a muttiple choice type questions areas follows + To.select your answer, click Gn the button of one of the options. + Ta deselect your chosen answer, click on the button of the chosen option again or click on the Clear Response button. = To change your chosen answer, click on the button of another option, and to cae save your answer, yous must click on the Save and Next button. + To mark the question for review, click on the Mark for Review and Next button. moo) Procedure fer answering 2 numerical answer type questions are as follows OOo) + Toentera numberas your answer, use the virtual numerical keypad displayed on Nt} the monitor. + A fraction (eg.-03 or -3) can be entered as an ansiver with or without 0" before the decimal point. «To cear your ans, ck onthe Clear Response buton and to save your «(GRE answer, you MUST click on the Save and Nextbutton. Virtual Numerical + Tomark the question for review, click on the Mark for Review and Next button, Keypad Ian answer isentered fora question that is Marked for Review, that answer will be considered in the evaluation. Formula for GATE Score of : Formula for GATE CE, CS, EC, EE and ME Papers Score of all Papers fier the oaluatono teense normalised mars based onthe Theformulor GATE soreofallpspersisgivenbelos pra gid Below ines elelted eonesponding to he mars obtained by a candidate for CE, C5, EC, EE and ME ; MEM. papa. Normalised markoff" candidate in session My jn gen S=S+ ES) oy, eM where, 5 = theGATE Scorofthecandiate, MC = the matkscbsind by the caida in he paper apared by thecandidatein GATE2013, session | apes, B= the average marks of the top 01% of the the man of marks of op 0.1% oF top 10 (whichever is candidtesconseringallsnsions larger) th candidates who apparent paper, the sum of mean and standard deviation marks of the candidates in the paper considering all (he average marks of the top 0.1% of the candidatesinthe session (82 sum of mean marks and standard deviation 5, = 90s tneScoressignsdia lt, S, = 380isthe ScoreassignedtoM, -M jsusuelly25 marks aut of 1000" pe, ahichever is ager. Heres the remand si the slandard deviation of marks of ll the caidas tho appeared the paper. i | \ \ | = theacualmasts cbined bythe canitucint® | ———M,= the qullying mark for general ctor cant in the | | | i i | wi g & a @ &g @eooeco co © Ge e@ e @ e GATE 2014 Cut-off Marks for Some Branches & Category wise BRANCH GENERAL“ SG/STPD “OBC (Non-Creamy) Total Appeared Computer Science & IT 25.0 16.67 22.0 1,55,190 Chemical Engineering 36.14 23.43 31.62 15,844 Civil Engineering 26671771 23.91 90,872 Electronics & Communication Engineering 26.56 17.08 23.01 2,16,367 Electrical Engineering 25:0 16.67 22.50 1,41,799 Instrumentation Engineering 250 16.67 22.50 22,387 ‘Mechanical Engineering 2886 19.24 25.97 1,85,578 Paper Codes for GATE + Aeronauticalterospace Engineering (AE) | * Goology and Geophysics (GG) + Agricultural Engineering (46) + Instrumentation Engineering (IN) + Architecture and Planning (AR) + Mathematics (MA) + Biotechnology (BT) | + Mechanical Engineering (ME) + Civil Engineering (CE) 1+ Mining Engineering (HN) + Chemical Engineering (CH) 4 + Metallurgica! Engineering (MT) + Computer Science and Information Technology f= * Physics (PH) «s) + Production ond industrial Engineering (P) + Chemisiry (CY) [+ Textile Engineering ond Fibre Science (TF) + Engineering Sclenee (XE) + le Science (XL) Ecology and Evolution (EY) + Electronics and Communication Engineéring «co + Electrical Engineering (EE) Recent Changes i GATE + Anew papet Ezoogy and Eroitin is introduced in GATE 2014 + Ezaminatons forall the 22 apes willbe conducted by an ONLINE Computer Based Test (CE, > GATE 2014 examination was held during forenoon and afteroon session on alternate weekends (Satnday and Sunday) 2014 between It February 2014 and 2nd March 2014. Examination for some ofthe papesin GATE 2014 was held in utile » pplication Fee has been revise again, Is €1500 for Male Candidates (GeneraVORQ),€ 750 for Women Candidates of anycategoy.®1500,or Other Candidates (Generl/O8C) and 750SC/ST/ PWD" Category Candidates Ferma cancidates are exempted fom paying the application fee. Candidates re requre toupload scanned copy of Photograph and Signature + TheApplication fee wasincreased from 1000to €1200. * Oniyfnal year students andpassoutstucents were eligible towite GATE eam. The application process was made completly online, candidates could view ther responses of the ORS and also GATE (Ofc leased oficial solutions for GATE papers * Fron 201 | onwards, four ofthe GATE papers can be attempted using computers through online mode. The our papers ae 2011 22292 ineeing paper code AE. Gesony ad Geophysics oper cole GO). Ming Eginering (pape code MN) and Textile Engineering (pape code TH) and Fibre Science, + From 201 | onwards, the GATE wl beheld inthe mocing (2-12) and afternoon (2-5 session, Als the computer based tests wil beheld on difrert dae, viiGATE 2015 Syllabus jr Chemistry Physical Chemistry rinciples and techniques; applications to a particle in a box, harmonic oscillator, rigid rotor and hydrogen atom; valence bond and molecular orbital theories, HUckel approximation; approximate techniques: variation and perturbation; symmetry, point groups; rotational, vibrational, electronic, NMR, and ESR spectroscopy Equilibrium Kinetic theory of gases; First law of thermodynamics, heat, energy, and work; second law of thermodynamics and entropy; third law and absolute entropy; free energy; partial molar quantities; ideal and non-ideal solutions; phase transformation: phase rule and phase diagrams — one, two, and three component systems; activity, activity coefficient, fugacity, and fugacity coefficient; chemical equilibrium, response of chemical equilibrium to temperature and pressure; colligative properties; Debye-Hilcke! theory; thermodynamics of electrochemical cells; standard electrode potentials: applications corrasion and energy conversion; molecular partition function (translational, rotational, vibrational, and electronic), Kinetics Rates of chemical reactions, temperature dependence of chemical reactions; elementary, consecutive, and parallel reactions; steady state approximation; theories of reaction rates - collision and transition state theory, relaxation kinetics, kinetics of photochemical reactions and free radical polymerization, homogeneous catalysis, adsorption isotherms and heterogeneous catalysis. Inorganic Chemistry Main group elements General characteristics, allotropes, structure and reactions of simple and industrially important compounds: boranes, carboranes, silicones, silicates, boron nitride, borazines and phosphazenes. Hydrides, oxides and coxoacids of pnictogens (N, P), chalcogens (S, Se & Te) and halogens, xenon compounds, pseudo halogens and interhalogen compounds. Shapes of molecules and hard- soft acid base concept. Structure and Bonding (VBT) of B, Al, Si, N, P, S, Cl compounds. Allotropes of carbon: graphite, diamond, C60. Synthesis and reactivity of inorganic polymers of Si and P. Fluid Mechanics and Mechanical Operations Fluid statics, Newtonian and non-Newtonian fluids, Bernoulli equation, Macroscopic friction factors, energy balance, dimensional analysis, shell balances, flow through pipeline systems, flow meters, pumps and compressors, packed and fluidized beds, elementary boundary layer theory, size reduction and size separation, fee and hindered settling, centrifuge and cyclones, thickening and classification, filtration, mixing and agitation, conveying of solids. Transition Elements General characteristics of d and f block elements; coordination chemistry: structure and isomerism, stability, theories of metal- ligand bonding (CFT and LFT), mechanisms of substitution and electron transfer reactions of coordination complexes. Electronic spectra and magnetic properties of transition metal complexes, lanthanides and actinides. Metal carbonyls, metal- metal bonds and metal atom clusters, metallocenes; transition metal complexes with bonds to hydrogen, alkyls, alkenes and arenes; metal carbenes; use of organometallic compounds as catalysts in organic synthesis. Bioinorganic chemistry of Na, K. Mg, Ca, Fe, Co, Zn, Cuand Mo.S © © e eS 2] © e © © © © e © © Solids Crystal systems and lattices, miller planes, crystal packing, crystal defects; Brage’s Law, ionic crystals, band theory, metals and semiconductors, Different structures of AX, AX2, ABX3 compounds, spinels. Instrumental methods of analysis, ‘Atomic absorption and einission spectroscopy including ICP-AES, UV-visible spectrophatometry, NMR, mass, Mossbauer spectroscopy (Fe and Sn), ESR spectroscopy, chromatography including GC and HPLC and electro- analytical methods (Coulometry, cyclic voltammetry, polarography — amperometry, and ion selective electrodes). Instrumental methods of analysis ‘Atomic absorption and emission spectroscopy including ICP-AES, UV- visible spectrophotometry, NMR, mass, Mossbauer spectroscopy (Fe and Sn), ESR spectroscopy, chromatography including GC and HPLC and electro- analytical mettiods (Coulometry, ‘cyclic voltammetry, polarography ~ amperometry, and ion selective electrodes). Organic Chemistry ‘Stereochemistry Chirality of organic molecules with or without chiral centres. Specification of configuration in compounds, having one or more stereogeniccentres. Enantiotopic and diastereotopic atoms, groups and faces. Stereoselective and stereospecific synthesis. Conformational analysis of acyclic and cyclic compounds: Geometrical isomerism. Configurational and conformational effects on reactivity and selectivity/specificity, Reaction mechanism Methods of determining reaction mechanisms. Nucleophilic and electrophilic substitutions and additions to rmuitiple bonds. Elimination reactions. Reactive intermediates- carbocations, carbanions, carbenes, nitrenes, arynes, free radicals, Molecular rearrangements involving electron deficient atoms. Organic synthesis Synthesis, reactions, mechanisms and selectivity involving the following- alkenes, alkynes, arenes, alcohols, phenols, aldehydes, ketones, carboxylic acids and their derivatives, halides, nitro compounds and amines. Use of compounds of Mg, Li, Cu, B and Si in organic synthesis. Concepts in multistep synthesis- retrosynthetic analysis, disconnections, synthons, synthetic equivalents, reactivity umpolung, selectivity, protection and deprotection of functional groups. Pericyclicreactions Electrocyclic, cycloaddition and sigmatropic reactions. Orbital correlation, FM@.and PMO treatments. Photochemistry Basic principles. Photochemistry of alkenes, carbonyl compounds, and arenes, Photooxidation and photoreduction. Di-r- methane rearrangement, Barton reaction. Heterocyclic compounds Structure, preparation, properties and reactions of furan, pyrrole, thiophene, pyridine, indole and their derivatives. Biomolecules Structure, properties and reactions of mono- and di-saccharides, physicochemical properties of amino acids, chemical synthesis of peptides, structural features of proteins, nucleic acids, steroids, terpenoids, carotenoids, and alkaloids Spectroscopy Principles and applications of UV-visible, IR, NMIR and Mass spectrometry in he determination of structures of Organic molecules.SOSGESOSHVSSCSCSSCOSEFL OFS LOSSLESS OHO90000009900 090- © 6 6 e © C6 6 6 © 6 e © e Solved Paper 2014 GATE Chemistry Online Time : hrs MM : 100 Read the following instructions carefully 1. There is total of 65 questions carrying 100 merks of hrs duration. 2, Questions 1 to26wilcary 1 markeach and questions 260 65 willcany 2marks each, 3. Questions 56 o 65 belong to General Aptitude (GA) type. Quostions 56 to 60 will cary 1 mark each and questions 61 to 65 willcany 2marks each. 4, The subject specific GATE paper section consists of 5 questions, 5, Unattempied questions will carry ero marks, 6. Wrong answers wil cary negative marks, For questions 1 to 25 and 86 to 60, 1/8 mark wil be deducted for each wrong answer For questions 261055 and6t to 65,2/8marks willbe deducted fr each wrong answer. 7. Thereisnonegativemarking for questions of numericalanswer type. 8. Non-programmable type calculator is allowed. Charts, graph sheets, and mathematical tables are not alowed in the examination hall (1 Mark Questions) 1. The maximum non-pV work that a system can perform at constant p is (aH (bo) ac (as (aaa 2. Consider the reaction, AtB==C ‘The unit of the thermodynamic equilibrium constant for the reaction is, (a) moll" (0) L mot (c)mol?L? (d) dimensionless 3. The number of IR active vibrational normal medes of CO, is, 4, The number of C, axes in CCl, is__. 5. The value of the magnetic quantum number of a prorbital is (@)-1 (o)0 (c)+1 (d) undefined 6. The molecular partition function for a system in which the energy levels are equispaced by e, is 1 1 Oye One i i 1 @— OT Oe 7. A monoatomic gas, X, adsorbed on a surface, follows Langmuir adsorption isotherm. A plot of the fraction of surface coverage, 8, against the concentration of the gas (XJ, for very low concentration of the gas, is described by the equation 1 (@)0-K1x) wo app AUX] (oo=K"*x 00 S 8. Ata given temperature and pressure, the ratio of the average speed of hydrogen gas to that of helium gas is approximately.2 | GATE Solved Paper 2014 Chemistry 9. An example of nido-berane from the following is (BH (0) Bt (0) Bathe (A)Bat se 10, The geometries of Ni(CO}, respectively are (@) tetrahedral and square planar () square planar and tetrahedral (c) tetrahedral and tetrahedral (6) square planar and square planar 11, The number of S—S bonds in H,$,0, is__. and [NiC],?- 12. In alomic absorption spectroscopy, the atomisation process utilises (a) lame (0) electric field (©) magnetic fl (d) electron beam 13. At room temperature, the number of singlet resonances observed in the NMR spectrum of MegCC(O)NMe, (N, N-dimethyl pivalamide) is. 414, Amongst the following, the metal that does not, form homoleptic polynuclear metal carbonyl is (a) Mn (o)Fe (0) Cr (d}Co 15. The reaction of (Cp, TaMe, II (Cp =CsHg) with NaOMe yields (a) [Cp,Ta(OMe),]! (b)[Cp,Ta(Me)OMe] (c)Cp,Ta(Me)=CH, — (d) Cp,Ta(OMe) = CH, 16. The complexes [Co(H1,0),Cl, JNO, and. {Co(H1,0), CKINO, ICI are (a) linkage isomers (c) ionisation isomers (b) positional isomers (@) optical isomers 17. The major product of the following reaction is, OH HO (i) MegS04,NaOH, HO. OH GHC, H0 HO Meo oH (a) mo (b) Met 0, MeO- “OMe MeO: OMe OMe OMe MeO OH (0)Meo- o (6) Ho Q Meo HH HO: OMe ‘OMe H 18. Amongst the following, the structure of guanosine 19, 20. is NH ¢ Cx (a) HO. a 0 OH OH H oo Ch (b) wow a Sn @ OH OH a =N & HN, Z " ® (0) Hox 0 one © OH OH 9 evr (HOY 9 N™ Ase OH OH ‘The correct order of IR stretching frequency of the C=Cin the following olefins is Oro I I tw (2) lla (O)ib>ti>t ()illsl>1 (a) ll>tatl ‘The correct order of the rate of solvolysis for the following chlorides in acetic acid is Oo Oo oy" I 0 mw (@) Ii>fotl (c)ilptotl (0) listi>t (a) tott>tt@ ©2000 0¢ a care zara | 3 21, Formation of the. product in the following (2 Marks Questions) photochemical reaction involves 9 K, 0 Ph, Pht Hf (a) disx methane rearrangement (b) Paterno-Buchi reaction (6) [2.3] sigmatropic rearrangement (2) Norrish type I reaction 22, The correct order of stability for the following conformations of cyclohexane is m +4 ee ()li>bil (a)bollstll(b)Iottstl (4) lll>iot 23. The major product formed in the following reaction is © tb) a) 4 H © ) at COeMe \COaMe 24, The overall yield (in ‘%) for the following reaction Pome riety FcOMe OH Jones’ wae, OH Ph—CHO— ae 90% LN le 80% g Beg py) eam pp 25, The most suitable reagent combination to effect the following conversion is Bud BO OH omn'— | OBn ‘Oo 0" {a) i. NaH, CS, then Mel, i. Bu,SnH, AIBN, Cy, reflux (0) i. l,PPh, imidazole: i, Hp, 10% Pd-C, ACOH, high pressure (©) i. Me,SiC\, pyridine, DMAP; fi, BugSnH, AIBN, CoH, reflux (@) i. MsCl, pyridine , OMAP; i, LIAIH, THF, reflux 26. y= Nr(6- Ze" cos®, is a proposed hydrogenic wavefunction, where Z= atomic number, radial distance from the nucleus, 0= azimuthal angle, N is a constant, The incorrect statement about y is (a) y =O in the xy -plane (0) two radial nodes are present in y (c) one angutar node is present in y (@) the size ofthe orbital decreases with increase in atomic number r= 27. The van der Waals’ constants a and b of CO, are 3.64 L* bar mol and 0.04 Lmol“*, respectively. ‘The value of R is 0.083 bar dm'molK~. If one mole of CO, is confined to a volume of 0.15 L at 300 K, then the pressure (in har} exerted by the gas is. 28. A plot of osmotic pressure against concentration (gL~) of a polymer is constructed. The slope of the plot (2) increases with increase in temperature (0) increases with increase in molar mass of the polymer (c) decreases with decrease in concentration of the polymer (@) decreases with increase in temperature 29, A platinum electrode is immersed in a solution containing 0.1 M Fe*and 0.1 M Fe*. Its potential is found to be 0.77 V against SHE. ‘Under standard conditions and considering activity coefficients to be equal to unity, the potential of electrode, when the concentration of Fe*tis increased to 1 M, is___. 30. Molybdcnum erytallises in a boe structure with ‘unit cell dimensions of 0.314 nm, Considering the atomic mass of molybdenum to be 96, its density (in kgm“) is___ 31. The ratio of molecules distributed between two states is 9.22 x10° at 300 K. The difference in energy (in kJmol"!) of the two states is__. 32. A Carnot engine operates at 55% efficiency. If the temperature of reject steam is 105°C, then the absolute temperature of input steam is__. 33. OF the following plots, the correct representation of chemical potential (u) against absolute temperature (7) for a pure substance is (s,l and g denote solid, liquid and gas phases, respectively)4 | GATE Solved Paper 2014 Chemisty 3 h 9 @H oy, g s T T oa of wl 7 7 34, The enthelpy of fusion of ice at 273 K is 41, The correct order of thermal stability for the 42, Amongst the following, the complex ion that is given compounds is (a) TiMe,>T(CH,CMe,), >TiEty (b) TiEt, > Ti(CH,CMe,), > TiMe, (c) TMe, > Tiét,>TICH,CMe,), (8) T(CH,CMe), > TiMe, > TEL, expected to show the highest magnetic moment at room temperature is atnwen, (b)|Fe(cn), (olcuro)?* (ICON @ 6.01 kJmol” and the enthalpy of vaporisation of 43, MinCr,0, is water at 273 K is 44.83 kJmol”. The enthalpy of sublimation (in kJmol") of ice at 273 K, is__. 35. Suppose y, and y, are two hybrid orbitals Vs =0.12V, +0.68 5p, +0.77¥ap, andy; = 0.123, ~0.63V5p, - 0.779, ‘The angle (in degrees) between them is___. 36. BCl, and NH,Cl were heated at 140°C to give compound X, which when treated with NaBH, gave another compound Y. Compounds X and Y are (@) X =BNHsCh and Y = BH, (©) X=BNHeCh and Y = BN He (6)X =BNGH.Cy and Y =BN Hy, (A)X =BNyCly and Y =B NH 37. The number of microstates in 'G is___. 38. The set of protons (underlined) in CHyCH,CH, OCH, that would exhibit different splitting patterns in high (500 MHz) and low (60 MHz) field "HNMR, is (2) CH,CH,CH_OCH, (0) CH,CH,CH,OCH, (6) CH,CH,CH,OCH, (4) CH,CH,CH,OCH, 39. Amongst. the following, the complex ion that would show strong Jahn-Tellar distortion is aylertio,)* (b) THO” (C)[CotHO)]* (IFeH OL 40. Amongst the following, the metal carbonyl species having the highest vq stretching frequency is (@)[Mn(0O, {b) Cr(CO), (o)[M(CO}Y (4) [Fe(CO), 7 44,Mg** is preferred in photosynthesis by 45. In Monsanto acetic acid process shown below, the 46. Formation of the ketone II from the diazoketone I (2) normal spinel with total CFSE of -15.5Dq (b)inverse spine with total CFSE of -15.5 Dq (c) normal spinel with total CFSE of -24Dq oS (¢) inverse spinel with total CFSE of ~24 Da, chlorophyll because (2) thas strong spin-orbit coupling (b) thas weak spin-orbit coupling @ (0)itis aheavy metal (¢) binds strongly with chlorophyf @ role of HI is CHOH +CO—RhO) catalyst, o41,.C0,H 180%, 30 bar (@) to convert CH,CH to a stronger nucleophile (CH,0") (b) to reduce the Rh{!) catalyst to a Rh(0) species: {c) to reduce a Rh (III) active species to a Rh(!) species in & the catalytic cycle & (d) toconvert CH,OH to CHI involves cL 2 PhCOOAg ‘0 Heat CO ‘Me Mé I 0 (@) generation of carbene and a [23}sigmatopic rearrangement (b) generation of carbene and an electrocyciic ring closing reaction (c) generation of ketene and a [2+ 2] cycloaddition (2) goneaon of Ketone and “a [Sa}siometnic rearrangement Se © 6 ® GaTE 2014 | 5 47. The major products X and Y formed in the 49. 'The major products X and Y formed in the following reaction sequence are Me Heat, RaneyNi, mah come * Seg 7 Y Me Me ,COMe COME x ff ye Phs- Me Me COME (0) X= vr ff HH PhS: PhS: Me Me (x oO. ve Che Ph’ 'COMe Me Me (xe oO Yr 7 Ps: ‘COpMe PHS co nMe 48. The major products X and Y formed in the following reactions are ae INaHl, Mel , AA “ ay following reaction bequence are is-stilbene 5 x. Bh is Cathy se oe (a) x= or EP “oO ~ O 4 (9) x= NS HH 50. The product of the following reaction gave 6 line in CNMR spectrum with peaks at 5 175, 52, 50, 46, 37, 33 ppm. The structure of the product is Ow Oe OMe MeOH ) w Deon OMe OMe ©) @) COpMe Come 541. The major product formed in the following reaction is HD Ph _H202 Ph’ Heat” SePh mS _ @) Pro (0) . D D, fe) oA i of Yn6 | GATE Solved Paper 2014 chemistry 52. The major products X and Y formed in the SOxMe following reaction sequeiice are (©) x Q ” CO-Me a 20 LOH 0 oO OMe a NO2 OMe oO im OL NOz wavelength (in nm) for the conjugated system shown below is, HO, fo) X= ‘Me HO (Use these absorption values for auxochromic groups alkyl: +5, exoeyclie double bond: +5, every additional conjugated C=C: +30) ae me bad eeded and Y formed in the 55, tthe m/e value of the detectable fragment formed Sete so uaenecenee area by MeLafferty like rearrangement of the COs Cb:—Cl following compound in mass spectrometer is__ MeOH, (equiv) CN Ho LT, 1:80,"* ag. NaiCoy ¥ as {d) x= 0 9 C20" Da) 54. Given the fact that 1,3-butadiene has a a UV absorption of 217 nm, the absorption 5 CO 5 ~ f ox (FT, General Aptitude (GA) Questions Meo ® (1 Mark Questions) CoH 56. A student is required to demonstrate a high level v= CL of comprehension of the subject, especially in the MeO” HN—Cbz social sciences. The word closest in meaning to comprehension is COMe ire r (2) understanding {(b) meaning - Ne (c) concentration (d) stability 57. Choose the most appropriate word from the optians or given below to complete the following sentence. ye One of his biggest __ was his ability to forgive. Z 2 7 HN—Cbi (@)vice —(b) virtues (c) choices _(d) strength &tate 2014 | 7 58, Rajan was not happy that Sajan decided to do the 63. The smallest angle of a triangle is equal to two project on his own.” On observing his unhappiness, Sajan explained to Rajan that: he preferred to work independently. Which one of the statements below is logically valid and can be inferred from the above sentences? (@) Rejan has decided to work only in @ group (0) Rajan end Sajan were formed into a group against their wishes (c) Sajan had decided to give into Rajan’s request to work with ie (¢) Rejen had believed that Sejan and he woutd be working together 59, If y=8x" +3, then the tangent at x=0, y=3 (2) passes through x =O, y=0 (b) has a slope of +1 (c) is parallel to the x-axis (d) has a slope of -1 60, A foundry has a fixed daily cost of Rs 50000 whenever it operates and a variable cost of Rs 800 @, where, Qs the daily production in tonnes. ‘What is the cost of production in Rs per tonne for a daily production of 100 tonnes? (2 Marks Questions) 64, Find the odd one in the following group: ALRV, EPVZB, ITZDF, OYEIK (@)ALAVX (@)z0F (0) EPvZB (@) OYEIK 62, Anuj, Bhola, Chandan, Dilip, Eswar and Faisal live on different floors in a six-storeyed building (the ground floor is numbered 1, the floor above it 2, and so on). Anuj lives on an even numbered floor. Bhola does not live on an odd ‘numbered floor. Chandan does not live on any of the floors below Faisa’s floor. Dilip does not live on floor number 2. Eswar does not live on a floor immediately above or immediately below Bhoia. Faisal lives three floors above Dilip. Which of the following floor-person combinations is correct? thirds of the smallest angle of a quadrilateral The ratio between the angles of the quadrilateral is B:4:bs The largest angle of the triangle is twice smallest angle, What is the sum, in degrees, of the second langest angle of the ériangle and the largest angle of the quadrilateral? 64, One per cent of the people of country X are taller than 6 ft. Two per cent of the people of country ¥ are taller than 6 ft. ‘There are thrice as many people in country X as in country ¥, Taking both countries together, what is the percentage of people taller than 6 ft? (230 (0)25 (o)15 (1.25 65. The monthly rainfall chart based on 50 years of rainfall in Agra is shown in the following figure. Which of the following are true? (k percentile is the value such that k per cent of the data fall below that value) = haa |) oo Sperarle SS prone dian Feb Mar Apr Nay Jin J Aug” Sep et Now Dec (1) On average, it rains more in July than in December. (i) Every year, the amount of rainfall in August is more than that in January. (Uf July, rainfall can be estimated with better confidence than February rainfall. (IV) In August, there is at least 500 mm of rainfall. (ei fand (®) land th (c) Wand itl (a) and iV’ Answer with Solutions . 1. (6} From first law of thermodynamics, AE=q+W The wok done W may be expansion work or ‘noin-expansion work. So, AE=q + Wopanson * Mfen sans 2 PAV + Men.emanson (+ Napanee OF q=AE+ PAV —Weapsraen Further, aS OF = AST TAS = AH — Whon expansion or When expansion = AH — TAS 1G (AG = aH-TAS) The non-expansion work is also called non-p¥ work oF useful work Thus, the maximum non-pV work that @ system can pertonn at constant pis AG. (@) For the given reaction, Thermodynamic equilibrium constant 0. _{C} K' fA} 8} where, {} indicates thermodynamic activities of chemical species and activities have no dimensions. Thus, K® is a dimensionless quantity. Note Equilbrium constant, which is equal to thermodynamic equilibrium constant divided by a Quotient of activity coefficient has some units for the gen reaction ‘8. For a linear triatomic molecule, The number of vibrational normal modes = 30 ~ 5 where, = number of atoms. =3x3-5=4 But this molecule has only 3 1R active vibrational normal modes due to degeneration of two modes as shown below, t t O+-c-—+0 O—C—O Asyrmetic ©—0—0 0++0-+0 2bending —Sasymmetic 2bending 4. CCl, is a tetrahedral molecule and hence have 7 point group. i, it contains four C, exes, 3C, axes and 66g mirror planes. 5. (0) The value of magnetic quantum number (nm) é depends upon the Value of / For p-orbital /=150, value of m for a pyorbital may be +1, 0 or ~1, depending upon the internuclear axis €.9., i 2 axis is considered as the intemuctear axis, value of m for Pyis 1 But it x or y axis is considered as internuclear axis, the value of m for p, may be O or +1, Thus, we can say foc a p-orbital the value of magnetic quantum number is Undefined, (@) The molecular parton function, if energy levels of a system are equispaced by e is given as & ‘Molecular partion function = t-e® (where, B= 7. (@) The general forrh of Langmnuit adsorption isotherm is KIX) é T+ KX] é For very low concentration of the gas, 1>>>K[X] * and hence, 1+ K(X]=1 G 8. We know that average speed, 7= ea é Since, 7, R and x are constant. 9. (6) General formula for nido-borane 18 ByHn.4 n= 4, formula of borane is By. Ifn=6, formula of borane is ByHig Thus, BiH is a nido-borane, ¢ 10. (6) In Ni(CO},, Ni is present as Ni. Ni =f Ar}8d®, 452,40 & CO being strong field igand par up thesectors — g with d-electrons making the s-orbital empty for hybridisation, ie., Ni in the presence of CO =Iared"®, 45° 4p? Thus, a Ni(CO},= 18d" fo} oso evel COCOCD) Sp°hybrcsation Thus, the geometry of Ni(CO), is tetrahedral and it is a diamagnetic complex,9983660 @ 8 © 6 6 6 eS e@eecocecrc@aecoeoooes Further, . in NiCig, Nis present as Ni, [Ni* =[Ar) 30°, 4°, 4p? 3d 4s ip ae [ CF being a weak field igand fs not capable to pair up the unpaired d-electrons. So, the avaiable orbitals for it are only 4s and 4p-orbitals. Ni in the presence of CI"=[Ar]3a°4s"4p° INCL, =[Aq) sd as 4p [RTT 14] be) beep] Two unpared &_S Cor e-—__sp*hybridisation {earamagnetc) Thus, it is also a tetrahedral complex. 11. The structure of H,S,0¢ is as Thus, in the above molecule, there are 4S—S bonds. 12, (@} To analyse a eample for its atomic constituents, it has to be atomised which is usually done by flame or electrothermal (graphite tube) etomiser. Other atomiser such as. glow discharge atomisation, hydride atomisation or cold vapour etomisation might be used for special purposes 18. The condensed structure of N, Nimethy! pivalamice is ce > (no adjacent C) Hg Number of singlet signals = Number of protons having no another set of proton attached with the adjacent carbon atom. In the above molecule, the number of such protons is 3. Thus, number of singlet signals = 3 14, (c} Among the given transition elements Cris the metal that does not form homoleptic polynuctear metal carbonyls. This is because of large M—M and M—C bond length or week M—M and M—C bond strength, (where, M-= transition metal and C= carbon). cate 2014 | 9 15, (c) CHO" being ‘strong nucleoptits simiuates a proton: Cra AME CHO'tat opr 16. (¢} The given two complexes give diferent ions when subjected to ionisation. {ColH,0),0,]NO, = [ColH,0),C1,)*+N eign [Coft,0},C(NO,)|CI = CotH,0},CNO,)I* +Cr Thus, these are called ionisation isomers. 17. (c) Monosaccharides like glucose when treated with dimethyl sulphate (Me,SO,) and 30% NaOH, form ‘methylated methyl glycoside. When the obtained ‘glycoside is treated with acid, the glycosidic methyl QrOup is hydrolysed to give free methylated suger. MesSOy H HO- 0 Ho. on NaOH 0% OH OMe Meo: Q Meo —Glycosidic g} Me group, one’ {r 0 OMe Me Meo-~ OH OMe 18. (d) The moleoular formula of quanosine is CygH,:NsOs ‘Thus, its structure can be represented as 9 NH OH OH 19. (c) Exoeyclic double bond have higher IR stretching frequency in highly stained rings because of increased s-character of C=C bond. Thus, the correct order of IR stretching frequency of the bond is aCe iy yy Uy) vem (17800Rr) (1678enr} (1651 orn")10 | GATE Solved Paper 2014 Chemistry 20, (0) In the soholysis process, the solvent behaves like a ‘ucleophile. Since, CH,COOH (acetic acid) is a polar protic solvent, but is @ weak nucleophile, soit favours §\1 process. Further, presence of an dlectron releasing atom like O stablises the carbocation intermediate of Sy1 reaction. Thus, the correct order of rate of solvolysis is Monet 21@ 0 Oar PO Fh Ph 4, 4iphony2, S-ojlohexadenone This reaction involves di-n methane rearrangement. ls mecharism can be represented as 10% ro? tnteraystom “Grossing FhoBn Ph Ph Ph Ph Ph Ph So) ($1.0 R*) Rearrangement, *_ Relaxation, Ph Ph a Ph Ph . a Ph Ph 22, (0) lis the boat conformation of eyciohexane, in which the tydrogen of G, and Ca, Cs and Cy carbons are eclipsed: Thus, in this molecule thete is a lot of torsional strain but no angle strain (due 10 tetrahedral angles). Hence, it is an unstable form, | is twist boat conformation. The non-bonded interactions between the two flag pole hydrogens are minimum and also the torsional strain due to eclipsing interactions on C,~Cy and Cs ~Ce are partly releived. Thus, it is somewhat more stable than boat conformation, {iis half chair conformation which have both angle strain and torsional strain, 50, it's the least stable conformation of cyclohexane. Thus, the correct order of stability of the given conformations of cyclohexane is i> i> 23. (c) The given reaction is a Diel's Alder type reaction Here, TICl, acts as a Lewis acid and catalyse the reaction by more activating the dienophile. Thus, aes 0 rao rates, 1, eco te mer oO come. cm Ph-CHO aa.NaoH ioe Ph” SMe 8% phy n 0% of 09x 80% of 0.72x9 = 09x 08 72x x08 072% = 0576x (Let the amount of PHCHO taken is 0) Overall yield (in 5) of reaction _0576x ox x100= 57.6% 820 5 I ,OH ae 35. oo tS Sin ne tusSt +> o y Lo Ze! ‘SMe l ue “oom ‘\4 | Ole os S—SnBle B20 820 a“ I f , ‘copa HBussn—> on ‘The reaction of —OH group containing compound with AIBN, HBusSn, C,H, reflux to convert i into —H is called Barton McCombie reaction or Barton deoxygenation.€ © 6 © 6 cS s) € eegoococoaoonoooooosn Thus, the correct set of reagents for. the given reaction is () NaH, CS, then Mel and (ji) Bu,SnH, ABN, Cela, reflux 26. (b) For the given hydrogenic wavefunction, n=Sand/=1 «Number of angular nodes ‘and number of radial nodes y=0 in ayplane and as the atomic number (Z) increases size of orbital decreases. 27. We know thet van der Waals’ equation for 1 mole of a gas is a &\v-)=Ar (0 + 3) w-d) On substituting values, we get 3.64 + SSF | (0.18 0.04) = 0.083 x 300 [> eel! ’ 364 884 ) (0.19 =249 (0+ 35) « c (0+ 2) 242 22608 0.0225)" 0.11 p+ 161.78 = 226.36 or p=226.36 ~ 161.78 = 64.58 bar 28, (a) The expression for the osmotic pressure is n=CAT When we plot x against C, a straight line is originated from the origin, slope of which is equal to AT. Thus, as the value of T increases, slope increases (here, F = gas constant or solution constan}. 29. For the Fe*"/Fe** electrode, E°,. .¢2 [Fe*]=0.1M, [Fe*]=1M From Nernst equation, =077V 0059, [Fe**] oe ne 2) Foro? [Here, n= 1, Fe* +6” —> Fe’ 0.059, (0.1) 2 Eogauggte 2077 - log Feat pgs O77 100") = 077 + 0089 =0829V Fase at GATE 2014 11 80, (1032.5) Given, atomic mass = 96 gol" Lattice type = bec for which Z = 2 Edge length, a= 0314 nm = 0314x107 m Z-M a No (where, Ng = Avogadro's number) . 2x96 (0314 x 107)? (6.022 x 10%) end “1.86 x10" = 1082.5 kgm 81, Molecular distribution between two states We know density, d= = 10822580 gemr* EET =o Nae ind AE NT In @.22 x 10° a 1.38 x 10° x 6.023 x 10 x 300 AE = 16.036 x 1.38 x 6.023 x 10° x 300 = 399 = 40 kimol"* $82, We know that efciency of Camot engine, = t~ 2 (Bron, n= 055% = 0.5 and T= 105 +273 = S7BK) os5=1- 98 q -378 os5~1=—38 qh 378 ~045 = 78 q 7-58 a0 045 83. (a) We know that (2) \ Thus, the plot between chemical potential (v) and temperature (7) for a pure substance can be represented as12 | GATE Solved Paper 2014 Chemistry 34, Given, 7 35, H,0 (s) 3 H,0 (N); A, = 6.01 kimot" 0 H,O() —H0(g), SH, = 4483 kimor (i) Enthalpy of sublimation of ice, i.e., #0(6) 9 H0(9), =? On. adding Eqs. () and (i), we get the required equation, AH = AH, + OH, = (6.01+ 44.83) kImol™ 50.84ksmol™ s-character = (012) x 100= 1.44% p-character = 100 ~ 1.44 = 98.56 First only the wavefunction of atoms are combined to give sp* hybrid orbitals with bond angle 120°. But s-character (1.44) is much less and p-character is, much higher as compared to thet present. in sp" hybrid orbitals, so bond order must lies in between 175 to 180°. 86. (@) When Cl, and NH{CI are heated at 140°C, they ive substituted borazines which on reduction with NaBH, gives borazine. orc BO, + SNH CIA By, Subsea borne NeBH, BNI ——9 BNHy oy) 0) Borazine 87. (9) For the term 'G, L=4 Possible m= £4 £3, +2, 210 H@s+t)=1 then s=0 Thus, tal number of microstates = total values of m, AA 38. (b) In the molecule CH,CH,CH,OCH,, C? is the carbon that is in direct contact of a group having e~ donating tendency CH, and also of a group having € withdrawing tendency (—CH,OCH,), that's why Proton attached to it behave differently in high (500 MHz) and low (60 MHz) field 'H NMA. 89. (@) The distortion in the geometry of the noninear molecular system is called Jahr-Tellar cistorion ‘Among the given, [Ti(H,0),]** because of 3d" configuration (or fg," configuration, a symmetrical coniguration) does not extibit this effect. But [Ce(HO)gF*", (ColHO)e]** and [FetH,O),)** because of their unsymmetric configuration ie, 42. (b, tag’ey in Cr®, th, 2 in Co and tf, 05 in Fe®, exhibit Jahn-Tellar distortion Since, this distortion in case of tp, orbitals is much weaker as compared to e, orbitals (as the former les in between x, y and z 8x28) 50, [Cx(H,O)q]* wil exhibit strong Jahn-Teller distortion among the given. 40. (2) The Vey stretching frequency is highest in case of [Mn(CO),]* because it possesses minimum electron density. As the electron density on the metal increases, it results in more a-back bonding tothe CO ligand, which weakens the C—O bond by pumping more electron density into the formally empty carbonyl ° orbital, This increases. the M—CO bond strength making it more double bond fike, Thus, results in decreased stretching frequency, 1, (0) An.easily available B-H ator makes the TiR, type compound less stable. Thus, among the given, TiEt, is highly unstable because of the availabilty of B-H atom and readily decomposes at ~ 80°C. TiMe, have no B-H atom, SO its quite stable and undergoes a-H substitution. at 40°C. TWCH,CMe,), has no B-H atom and also it is a sterically hindered compound, so loss of B-H is much more dificult. Thus, itis most stable among the given and decomposes above 100°C. Thus, the order of thermal stably is T\(CH,CMe,), > TiMe, > TEt, c} Magnetic moment, 1 = y/n(n+2) BM where, n= number of unpaired electrons Thus, the species having maximum number of Unpaired electrons, show highest magnetic moment at room temperature. In [Ni(CN),]?* Ni = [Ar] a 4s. 4p Tae t he} fx) fexpod “Tower OF OF OF 0 4p +e bxpopol2028609 ecoooocrecoonaoeonosgego0eoc ee nat In (Cu(t,0),}*, Cu* =[Ar] ad 4 Wet] be} fededo} pope] Ome unpaired eee ° nat In [Co(CN),]**,Co® =[Ar] ad 4s tp tO] tee] fod fexhexfe] ungated uo ° n=0 43, (c} InMnCr,0,, Mnis present as Mn®* (d"-configuration) and Cr as Cr** (d° configuration). Since d® and 0% ions have strong preference for octahedral geometry ‘and d” has more preference for tetrahedral ‘geometry, thus the divalent Mn?* ion will occupy the tetrahedral voids and the trivalent Cr will occupy the octahedral void in the close packed structure of oxide ion, Thus, MnCr,0, is a normal spinel (in which divalent jon occupy tetrahedral voids and trivalent ion ‘occupy the octahedral voids). T eg 1 ; spities \O TATA] A] t29 CFSE =(-04x3)+0 4.2=12 Dg Teahedral splting CFSE 2441 12 Da) + (1 Net CFSE 44. (b) in photosynthesis, Mg” is preferred by chlorophyl as itis a light atom with a small spin orbit coupling constant, 50 inter system crossing is inhibited which favours the energy transfer from the excited singlet state. Further, itis not a redox metal and does not interfere in the charge separation step. GATE 2014 | 13, 45, (d) The cyclic representation of the process is as AL ant At Ie co 41. ° os 48. (b) When SW ct I's gy follows. IK aco] Sai 1 Noo HaQ, HgC- ipa X ate aod i Hy | HC Ico ish od CH] From the cycle, itis clear that Hl is used to convert CH,OH into CH 0 ez! ~ {3;3)S:gmatropic rearrangement on | ‘sAKer reaction Me owe dae] -HSPh (reduction) RanoyNi 250 CO;Me .COgMe Phs- ” 3) CO is treated with Mel at 25°C, the 4 substitution occurs at the pyridine ring but in the presence of NaH substitution occurs mainly at pyrrole a44 | GATE Solved Paper 2014 Chemistry “(9p cis-stibene = le nate (0xidation) (yy =2HI oe Par Ne oe Ne ° y MeOH J ' “=o OMe Because of the presence of six carbons in different environments cae Disrotaloy slecoyciaton 50. ©) (ie, sik types of cartons as represented by 4,b,¢,d,.....) the obtained product gave st peaks in °C NMR spectrum, BL WP ne Hide al Pri SePh ° Selenoide ion Pro? Syn elimnaton Ph Smaliination Tans product (under mid (only possible conden) (on poss 82.) 10H \nost 80 ER Ang, foe idk, 53. (b) woh g oxime Conversion of X into Y by using TiCs/H,0 is called nef reaction on HeSOu + MeOH, etcaton Ho NH rou ¢ mes) eG Cbz—O1(tequi) yo OMe ‘27 NANOS © i i, * dove NH—Cbz (Sibstvon occurs preferentially at N atom) i € S Exooycie doublebond Base value of 1, 3-butadiene = 217 nm ‘Additional conjugation = 30 x 1= 30 Exooyctic double bond =2 x § = 10 ‘Alkyl substituent Ring residue = 4x § = 20 Total = 282 nm & e@ @@o09 @©0e0 8090 ® ® @eooooeone 9 @eeoegoed 55. Straight chain cyanides undergo hydrogen. rearrangement in a six membered transition state and, give a % i at mie 41 * os a 1 he Sons —+ fl 1 ‘Se He mie=41 C, Scle 156. (@) The word closest in meaning to comprehension is, the act or fact of grasping the meaning ie, Understanding 57. (b) Virtues means moral excellence and righteousness. 5B. (d) As we know, Rajan was not happy that Sajan decided to do the project on his own. It means that Rajan had believed that Sajan would be working together. 59. (0) Ity=57 +3 leo So, tangent at x=0, then it is parallel along the axis, 60. Fixed cost = 50000 Variable cost = 800 = 800 x 100= 80000 So, production cost of 190 tonne ixed cost + variable cost 0000 + 80000 = 130000 Cost of 1 ton 100, 61.) 62. (b) elas 5} Chandan 4} Faisal 3} Eowar 2} Anuj 1 fp GATE 2014 15 63. Lot the angle of the quactilateral be x. $0, 3:4:5:6 ie, 3x 4x-+ 6x +6x= 360° 18x = 360° x= 82 La9° 18 :. Angle of the quadrilateral = 3x 20° =60°, 4x20°= 80°, 5x20" = 180°, 6 x2 The smallest angle of a A is equal to two third of the smallest angle of a quadtilaterat 2 ie, £xeor= 3 The largest angle ofthe A is twice the smallest angle. ie, Xp=2 x60" = 120" Thén, third angle of a A = 180°-(120° + 40°) = 180° - 160° =20" :. Sum of secone! largest angle of a A and the largest angle of the quadflateral = 120° + 40° = 160° (6) 1% ofthe people of county X are taler than 6 ie. 400 3 oF he peopl of county Yar tar than Ge, 100 50 Then, there are thrice as many people in country as in country ¥ ie, X = 3Y. Taking both countries together xy fa iw" 50 =e 2 X=3Y] “100 * 30 _sY 100 According to the given problem, we get sy 100 x 49928” 4Y 00% a¥ => x 100=1.25 400 Hence, the percentage of people taller than 6 tis 128 65. (b) () After analysing the graph, we see that on average rainfall i.e., 650 rm, the rain more in July than in December. (i) In duly, approx 650 mm rainfall, while in February, ‘80mm approx, which can be estimated with Confidence in July 8s compared to February rainfallGATE Chemistry Solved Paper 2013 ‘MM: 100 ‘Time : hrs Road the following instructions carefully 1. There is a total of 65 questions carrying 100 marks, 2. Questions 120 25uitcarcyt markeact and questions 2510.5 wll carry 2marks each. 3, Questions 48 101 (2 pairs) are common data questions and questions pairs 52-58-54. 55 are tnked answer type questions. The answer tothe second question ofthe linked answer type questions depend on the answer tothe frst «question of he par the fst question i the lisked pairis wrongly answered is unattempted, then the answer to the second question inthepairwil note evaluated, 4, Questions 56 065 belong to General Aptitude (GA) type. Questions 56 to 60 willcary 1 mark each and questions 61 to€5willcary 2marks each. ‘5. Unattempted questions wil carryzero marks, 6. Wrong answers il cary negative marks. For questions 1 to 25 and 661060, 1/3 mark wil be deducted for each wrong answer. For questions 26 10 51 and 6! to 65, 2/9 mark wit be deducted for each wrong answer. The question pairs (questions 52 and 63) and (questions 54 and 65) are questions withlinked answer. There willbe negative marks only for wrong ansveta theft question ofthe inked answer type question pari. for questions 52 and 84, 2/3 markwibe oducted foreach wronganswe. Thereis nonegative marking for questions 53.and 86, 7. \nnumerical answertype (1 Mark Questions) 1. The point group symmetry of HyC=C—=CHy is (2) Don (©) Coy, (c) Coy () Deg 2. Two ‘tril wave functions g=e(a-a) and =e lo-xitox7(a-xF give ground state energios B, and Ep respectively, for the microscopic particle in a LD bor by using the variation method. If the exact ground state energy is By, the correct relationship between By,Z, and By is (2) Ey=E)=Ep (0) E <6) =E; 3. ‘The ground state energies of H atom and H, molecule are ~18.6 cV and -31.76V, respectively. The dissociation energy of Fis _w. 4, A2L vessel containing 2 g of Hy gas at 27°C is connedted to a 2 L vessel containing 176 g of CO, gas at 27°C. Assuming ideal behaviour of Hy and CO, , the partial pressure of Hy at equilibrium is bar. jestions, to enter anurnber as your answer, use the virtual numerical keypad. 5, Consider the reaction, 20(s) +0, (g) =E 2CO(g) dt equilibrium. ‘The equilibrium can be shifted towards the forward direction by (2) increasing the amount of carbon inthe system (0) decreasing tne volume ofthe system {c) decreasing the pressure oft system () increasing the temperature ofthe system 6. A sparingly soluble electrolyte Jf)X ionises as M,X == 2M* +X The solubility product (Keg), motal solubility (S) and ‘mean molal activity coefficient (y.) are related by () Ky 24532 | Chapterwise GATE Solved Papers e Chemistry 7. For the first ordex consecittive reaction P+ O-> R, under steady state approximation to (QJ, the variations of (PJ, (@) and (R] with time are best represented by § § @ § ®) § 8 g § & 5 t (c) 5 (d) 3 3 8 8, At 278 K and 10 bar, the Langmuir adsorption of a gas on a solid surface gave the fraction of surface eoverage ss 0.01, The Langmof adsorption isotherm content bar", Give the answer to the third desma BRT 9. Conversion of boron triftuoride to tetrafluorobo- rate accompanies (a) increase in symmetry and bond elongation (b) increase in symmetry and bond contraction {c) decrease in symmetry and bond contraction (@) decrease in symmetry and bond elongation 10. The correct statement with respect to the bonding of the ian MesN and Mey? ‘with the metal ions Be? and Pa" (@) th igands bind equal strong with both the metal ions as they ate dicatonic (b) the ligands bind equally strong with both the metal ons as both the ligands are pyramidal (0) the binding is stonger for Me,N with Be®* and MesP with Po? (4) the binding is stronger for MeN with Pd? and MegP with Be?* 44. A crystal has tho Iattico parameters a#6#c and a=P=7=9. The erystal system is (a) tevagonal 4) monacinic (€) cubic (6) orthorhombic 12. ‘The by-product formed in the characteristic reaction of (CosCr= CCOMo)Me with MeNH is (@) co (©) MeOH (@) MocHO (6) MeCONH, 13. The catalyst and co-catalyst used in the Wacker Process, respectively, are (@) Pdol, and Cu (© Pa and CuCl (&) CuCl and (PaCl,]? (@) (Pacl,]?* and CuCl, 14, Oxymyoglobin Mb(O,) and oxyhaemoglobin Hb(O; ), respectively, are (6) paramagnetic and paramagnetic (©) ciemagnetic and diamagnetic (€) pararragnetic and ciamagnetic (@) clamagnetic and paramagnetic 15. Hapticity of cycloheptatrienein Mo(C;Hy (COs is 16. The number of oxygen molecule(s) that « molecule of hemerythrin can transport is 47. the maximum numberof sare isomers posible for the compound given below is Me te 9 We OH NO, NO 18. ‘The correct sequence ofthe amino acids pressnt in the tripeptide given below is so Sl ar (a) ValSer-Thr (6) Leu-Ser-The (b) VatThrSer (0) LeuThrSer 19. Among the compounds given in the options, the one that can be used as a formyl anion equivalent (in the presence of a strong base) is (@) ethylene (6) nitroethane (6) 1, 3cithiane (@ 1, 4- 2X0, (g) at 298K, given the values, AU =9kJ and aS = 84JK™, AG is (@) 11.08) (0) #11.08 ks (6) 1355 4) (@) + 3554s 36. The change in enthalpy when 3 mol of liquid benzene transforms to the vapour state at its boiling temperature (80°C) and at 1 bar pressure is ki. 37. The moment of inertia of a homonuclear diatomic molecule is 75x 10° kg m. Its rotational partition funetion at 600 K is 3B, Fora reaction of the type X Y, the correct rate 4 expression is (XJ) and {X] correspond to the concentrations of X at time 1 =Dand ¢=t, respectively) res at (a) Xo — ty #2) 1X1 pd 0) =; + HeED=hy (Mo ct MG +f, - hd 91) (0) -oF © b Reh X1 ~ ky Xo 39. The temperature dependence of partition functions are as follows Festa * T”, Yoeatin * T° droatin 7 (linear molecule) Groation * TS” (nonlinear molecule) ‘According to the conventional transition state theory (CPST), the temperature dependence of the Arrhenius pre-exponetial factor for a reaction of the type given below is linear molecule + linear molecule = non-linear transition state - products (7! (py 7? or (a) 7? 0, According to polyhedral electron count rule, the structure of Rhg(COhg is (2) closo (0) arachno (b) nido {a} hypho 41. Decarbonylation reaction of —[ets-(CHJCO) Mn("CO)(CO\] yield X,¥ and Z, where X=((CH,)Mn(CO}]; ¥ =[cis-(Cl,)Mn (COKCO), |; 2 = trans-(CH,) Ma (°C) (CO TT Solved Paper 2013 | 5 ‘The molar ratjo of the products (X:¥:Z) in this reaction is Greist (12st) tst:2 Mata 42, The increasing order of melting points of the halides NaCl, CuCl and NaF is (2) CuC< NaCl .Cp,20v, od t 2Gy's are subsidiary axis which are perpendicular to principal Cp axis passing through all three carbon atoms. Hence the point group is Day 2. (@) Given that one (@-%) gs.=E, bo =0x@- x) + 00x? (a— xF* 9S=E, Enact ground state energy = Ep For microscopic pertcl in -D box we know that ‘and % error calculated for both these trial wave functions by using variation method are 0.125% and 08%. ‘As given in question 9% error Oey 0.125% b= Wt We 0.125+ 0.5= 0.825 s. True ground state energy of dis less than true ground stale energy of 6; Fy M9 =1 and according to Le-Chatelo principle the equibxum shift in the direction where number of gasoous particles is minimised which can be done by decreasing pressure of system only MX we OM + XP- ss Kop =BS ta Sys K % 7. (@) According to steady state approximation, the concentaion of intermediale remains constant throughout the reaction but. reactant concentration decreases and concentration of product increases. as the teacton proceeds hence the graph showiag concentration of P,Q. and are beter represen in onion (9) 8, Rate of adscepion = ate of desertion (at equibium) Ka(t-0)P =Kd 0 ka (0 Kg 6. id) 9 (4) bar =0.0010 bar” * 7-o0i)*i0 Langmuir adsorption constant (K)= 0.0010 bar~* 9 (a) F : we 4 \ elie Tiltueraborane Number et sym operations 4 3212 {Fer Dyh point rou nurber of symmety operation = 4] Here number of symmetry operations in hence, increase in symmetry occurs §©3000 0_ 6 6 eS 10. (€) According to HSAB concept (Pearson theory) Hard acid has a tendency to combine with hard base and soft acid has a tendency to combine with soft base inorder ta give the stable product, hence bond is stronger. tiMo3 + Be?* — Stable product Herdbase Hard acid PMe, + Pd?* —> Stable product Sofibase Hard bese 11. d) a=B=7=90 ay These parameters denotes the orthorhombic crystal Seton en es ak, pis oo ate ty = oN Me o0/INoo ite co co of co i — 0 te oH yt “MOH °C Co Ne 13, (d (PCI, is used as catalyst curing the reaction which transforms to Pd (0). Co-atalyst CuCl, is used to convert Pd (0) to Pa (th 14, (b) Oxyrnyogiobin Mb(0.) contains Fe (I) prosent as low son ie ne No unpaired electron, hence diamagnetic. Onyhaemaglobin Ho (O;)4 contains Fe (I) as low spin, oo n=0 No unpaired electron, hence diamagnetic 15. According to 18 e° rule, any molecule will be stable if and only iit contain the 18 6° to its outermost orbitals Let us consider hapticity of CHa = x and it follows 186° rule Mo (Crt) (CO, Contribution of Mo= 6 Contribution of (C0) = 2 For Mo (CH) (CO), 6442x3218 x=18-1 Hapticity of CHa =6 Solved Paper 2013 | 9 16. itis anon haém protein used for oxygen storage and contain two Fe (ll) atoms. 1 trai, ure onygen molecule . wig Me OO7 NOz NOp ‘There are 2 types of chirality presenti this molecule () Axial chirality due to chiral axis, (Chirality due to centro (*) Hence total number of sterao isomers =2? = 4 17. Chia axis 18, (2) Given tripeptide are mado up by combination of three amino acid valine, serine and threonine sequentially. oH “i ¢ “ HN7ScOOH HANCOOH —H,N~ScOOH va ser - 19.6 Cs lH,O O we (OY Base, HaCieHO Formyl “ ‘ti é 13) aithanes SHH This is why 1, 3 dithiane may be used as a formyl anion equivalent in presence of strong base 20. (a) Oe 1.Me;Cuui, £40 sane J) fall 's reagent “ke oH 9 + 5 “Me 7 “ye () Gilman's reagent causes 1, 4 addition due to HSAB concept. (i) I attacks from back side due to steric hinderance offered from top face by -buly. group. 24. (a) This reaction is an example of Hotimann bromarnige reaction which convert amide to amine having one carbon atom lesser than amide.10 | Chapterwise GATE Solved Papers # Chemistry 23. (t) This is an example of chichibabin reaction and major product is 2 amino quinaoline. This is a nucteophiic substitution reaction occurs at 2nd_ position of auinolne CO = COC. ¢ eAm 2 amino quinoline 24, There are 5 ctferent kind of carbon, hence gives five ECNMR signals 25. (@) Sharp band at around 3300 em” is given by terminal alkyne due to C =:C-LH streaching. 2 butyne has no ee does not give sharp band at 3300 om”? in IR spectum, 26. PRs ® Meo. on | Meo, i . Nu fia ya +CO, o 2 x pe on ¥ z | $6 (R= cyclohexyl) & NH, H— Cyt RUPLCLCagtre 20 +17 +16 .cooH 7 Fig. Hoffman bromamide Reaction 180 + 3=213 My =101+ 95.5x2 443x124 72x 14 31x2 22. (d) 33 sigmatropic rearrangement is a characteristic 1014714 62+ 49x 12+ 72x t= 822 property of 1, § hexadiene. It occurs by breaking of 432 1-1 bond as shown below. I! and Ill are the sane Number of moles of X =—— = 0.021 ‘structure. 213 Number of motes of ¥= 822 x 19°%g = 0.001 mol ro Mol % of Y=——0001 0001, 499 Toot 0021” 0.02% 100 =a 4.99 2 27. (a) Analysis of IR data = 1760 m7 * Indicates presence of carbony group HNMR : 3 (ppm): 7.2 (1 Hd, J =16.0 Hd) —— This 2,4 value of J is due to trans Hydrogen coupting 5 3 5.1 (1H, m) 2.4 (BH, S) < due to 3H of CHy oo 18 (4, J=7.0H,) mM °qNMIA 8 = 170 ppm due to carbory! carbon,Solved Paper 2013 | 44 @ 0 O_ 72, BM 29. (a) The two fact should be kept in mind beter weting tne mechanism, of feacton PinacoHPinacolone 6 [lf tredenet rearrangement Me “H54 () Stablity of carbocation 18 (i) Group anti to OH will migrate itramoleoularly Value of J = 16.01H, is characteristic value to identity the desired structure. 28. (d) H nine de JO. TCL r N pyrgine t, 20" “7P Aven) Me ne Intramolecular migration of p-mthy phenyl eoours. Firstly we see more stabilty of carbocation. So OH ot 2 undergoes dehydration, not OH of C-3 because " HNO, [en ent oy oo" Reaction proceeds via diazotization leading to formation of diazonium salt followed by alkyl shift and hydrolysis to give the desired product. 31. (@) Wess .Ph Messi. Ph ve enyeno—- NOY myer ° gar reagent Sr Ho MesSi_ OH Messi. é a > 7 Ph Ph K Ph Ir Mey OH, H H K Ph Ey elimination Pr Yen PMA, z E Majoe E alkene ocours as major product because the bulkier phenyl group are trans to each other 32, 0 (0 ~(). (H) ~ (9) i 2a aren One® sytem Be a ° on rotating We motecue™ Ss 2 33. @ y=0"% ara h-(% 10°) her )=ae*) 1 eigenvalue 34. (0) Given ¥ =2885 om"? [e-em Sheet moe os goed 8s? La] wee"? fax 4x) xe" + 4x02") . “eee 22 = 16x? 7% — 4"? — 16,2272 Here We know that, zero point energy of malecul bE =1x6625% 10 Js x3x10%ns"! x 2885 om ea ss rt EID, 662532685 24 2.8669% 10x 10" 35. (a) Given reaction i ¥,04 (1) —> 2X05 (9),T =208K AU =9KJ and as = 84 Jk" AH =? Ang =2-0=2 € AH= AU + Ang RT =9kJ+ 2x 8.314% 298 (9000 J+ 4955.144) J = 13955144 J AG = AH -TAS = 19955-144 J— 298 kx 84 Jk™! 19955-144 J~ 25032 J ~ 11076.886=~ 11.08 kd ‘According to Troutons rule, entropy of non associate solid is 87 J mol” ,n=37 =80+273=353K nas She = MMyy <8 8 %Ty =3X87 953 ib =92133J mol"? = 92.193 kJ mole” 1k37. Rotational partition function may be calculated by using folowing formula, kT _ ete aT AT AT) fa Sa ot ant oa ae where 6 = atomicty. Here His cfatomic. 5 o=2 Given =7.5x 10" ® kg m®. Now, we can calculate Eee as ,, BX (:14P x7.5x 107 © 1.38% 107% 500 2x (6.626% 10° 4)? 8X 985% 75x 1.38x 5x 10° x 102 2x (6.6267 x 10" # 8x 9.85x 7.5x 1.38% 10° _ 4077.9 10" 2 (5626F 87.1828 = 46.77 x10? = 4677 J 38. (0) Rate of reaction = rate of forward reaction - rate of backward reaction ~ St KM (Mp = OOH +h he Hep ~F = 0 halk Ma Fy + NM ~ he OM 8 39. (@) We know that K=A.e [? Taking log on both sides log K =log A-—2 1 logon both sdeslag K =log AF 5 =log k + £2 E, Azlog k +52 plameuedhl, Here we can analyse that Ahas the inverse relation to T SoA T~' inthe correct choice. 40. (a) According to polyhedral electron count rue, sumber of clectrons present in Ah(CO)ig = 6x 94 16x2 Electron count Total numberof valence electrons present on compound 12x number of metals 2 Solved Paper 2013. | 13 Since 7=n +1 where n=6 (6 Rh atom) The compound belongs to closo structure. 41. @) "C0 is removing 0 | Noo \, z rea co i 20 OCr| Cy re Hs is mn Ma | IN, Nau oo | Neo oc’ co. cot co a 0 Hs iy, trans product 25% pect us woeapcta C0 without CO = 25% ‘3 oo Neo ™ cx alae Hence % of¥ (in product) = 25% © 25% = 50% 42, (a) As we know, more ionic crystal have more melting point and we also know that more is the electronegatiiy dlfrence more isthe ionic character. ‘Among the folowing we can observe that CuCl Covalent NaCl & lonic NaF © More fonic 43. (@) Electronic configuration of (Gd is = [Xe] 4” ‘This electronic configuration is only due to extra stable half led electronic coniguration Navi] he eA MEAT L=0, 27/07 No LS coupling because n= nne2)= 7743) =7.98M 44. (0) VHD@lF* has V2* metal having 3d° electronic, Configuration due to which it has maximum negative value of CFSE out of al. Hence has maximum enthalpy of hydration. Mettng point increases 6314 | Chapterwise GATE Solved Papers e Chemistry Gn CFSE = -04=- 1.2 by Mn?* =d°, CFSE =0 OP nal tag eg” OFS =3x-0.44 0,6=- 1.24 06-064 Greater the negative value of CFSE greater will be its hydration energy. 5, (8) Shortest distance 4 6. (@) Potarographic method is based on the voltamettic measurement by combined diffusion mass transport using concept of difusion current. Both metal ions have diferent standard electrode potential hence they wil produce different extent of diffusion current and causes different diffusion mass transport hence they can be analyses using diffusion current, 47. (9 NP =30® 240 4a HWA 7 2414223 Tem=F 2 t=4 Fig. Orgel diagram of d®-Oh compound 48, (8) According to exclusion principle {AV xT = constant mag He eed > = AT = temperature f As temperature increases width decreases hence an 150°C width is lowest. es These two form aceurs in dynamic equioium at high temperature, and the difference between these 6H of cs two mettyl cannot be identified hence at high temperature sharp signal wil be obtained forthe 6H Chemical shift of two CH hydrogen are at 2.87 and 297 «Difference in frequency = AV ‘AV = (Chemical shitt diference between 2 single!) x; frequency of machine ) 97 =2.87)ppm x 300 MHz =010 x 900 MHz xppm 10300 108 x10" AY = 30H 49. 50. (6, This is @ common method of preparation of borazine| also known as inorganic benzene. NH, Clt NaBH, —> NBH, it Ammonium chloride on heating with sodium borohydride gives N.B:H, fi - j € os, a HB BH Te S74 \ A Fig. Structure of Borazine90 OL SSEeeoeoooe of eS 7G O06 @e@ecooeoo ao 51. (d) Because the compourit contain Nand B as. cyclic member of heterocycles and have 6x electron cloud (Compound is known as borazines. 52. (@) Formation of cycc aoetal occurs from the same face only. Because of steric hindrance trans diol cannot Undergo cyclic acetal formation, Ho, IH - oH 53. (@) MnO, causes allyic oxidation and acidic hydrogen causes deprotection of cyclic acetal FBaiis | PePretection 54. (b) Half-cell reactions are given below 1.Fe —» Fe®* + 36° EF ppgae 2+ 0.096 2, Fe (OH) +3e° —+ Fe + 30H" Ere(ooyire = 8788 Qn (1+ @)=> Fe(OH}; —> Fe*+ + 30H® E°=— 0786 + 0.036 =(~0.750 V) This can be represented as (FelFe®* fall oH® faq)iFe (OH) (6) Fe) Oxidation half cell Reduction half cell 55. (d) Nemst equation for above reaction may be written es, RT Fat = 710 Key lode Kig = EXE = 0.750% 3x 96500 ee RT 8.514% 208 217125 87.63 ed Paper 2013 | 15 lowor numerator: _y TOOT NUMEFEIOT Igyor value iigher denominator 56. W2 Ca? > Zn? (b) Zn?* > Ca?! > Mn? (@) Mn?* > Zn?* > Ca?* (d) Zn® > Mn? > Ca** 15, The number of terminal carbonyl groups present in Fe (CO), is [1 Mark] fa) 2 (b) 5 (6 @3 16. The plot of xT versus T (where, 1, is molar magnetic susceptibility and T is the temperature) for a paramagnetic complex which strictly follows Curie equation is {Mark AL “A dy an @ @ @22860 0. 200008368 @22@8 ©®oo @eooeonoot 8 GATE 2012 17. The IUPAC nomenclature of NalPC\,] is {@) sodium hexachlorophosphine (V) (b) sodium hexachlorophosphate (V} (€) sodium hexachlorophosphine (d) sodium hexachlorophosphite (V) [1 Mark} 18. Consider the following pais of complexes [CoF(NH,);}?* and [Cr{OH, ), 1?" [Co(NH,};(OH, ))* and [Cr(OH, }, 7° [Co(NH},]* and [C(OH,),]?* [Col(NH,) ,]* and [Cr(OH, )g]?* The electron transfer rate will be fastest in the pair (2 Marks} (a) [CoF(NH,) 1 and (CHOH)),]* (b) [Co(NH,),(OH, J] and [Cr(OH,)}* (c) {CotNH,),]” and [CrOH, ),]?* (@) {Col(NH,)s}** and [CrOH,)g1°* 19, The extent of Mossbauer quadrupole splitting of iron follows the order (2 Marks} {a) FeCl,- 4H,0 > K,[Fe(CN),(NO)] > FeCl;-6H,O (b) K,[Fe(CN) (NO}] > FeCl,- 4H,O > FeCl;-6H,O () FeCly-6H,0> K, [Fe(CN),(NO)] > FeCl, 4H,0 (d) FeCl,- 4H,0 > FeCl, 6H,0 > K; [Fe(CN) ,(NO)] 20. Haemoglobin is an oxygen carrying protein. The correct statement about oxy-haemoglobin is that (2 Marks} (a) the metal is low-spin in +3 oxidation state while dioxygen is in} form (b) the metal is high-spin in +3 oxidation state while dioxygen is inO3 form {c) the metal is low-spin ini +3 oxidation state while dioxygen isin neutral form (d) the metal is high-spin in +3 oxidation state while doxygen is in neutral form 21, The ground states of high-spin octahedral and tetrahedral Co(l) complexes are, respectively [2 Marks] (@) “Toy and “Ay (b) “Ty and 4A, (c) *hy and *A, (@) “Ty and *, 22, The incorrect statement about Zeise's salt is {a} Zeise's salt is diamagnetic (b) The oxidation state of Ptin Zeise’s salt is +2 (©) Allthe Pt—C| bond lengths in Zeise’s salt are equal (d) CC bond length of ethylene moiety in Zeise’s salt is longer than that of free ethylene molecule [eMarks} 23. The number of possible isomers for the square planar mononuclear complex (NH,) MCN) ] of a metal Mis fettarks] @2 4 6 (3 Chemistry | 3 Chemical and Ionic Equilibrium 24, Ifx4 and xp are the respective mole fractions for A and B in an ideal solution of the two and Ty, Tp, T are the fusion ternpesatures of pure A, pure B and the ideal solution respectively, then [1 Mark} WAH say (11 b-45 ef ze wm (t ] eel oP tastes (11 bi-a sonf mG AH ey (11 er z 6 (-2] —AH®, ) 1= xy = exp) — (1 _ R Wh \ 25. Among the following donors, the one that forms most stable adduct with the Lewis acid B(CHs), is [1 Mark) fa) 4-methylpyridine (b) 2, 6-dimethylpyridine (0 4-nitropyridine (6) 2, 6-di-tert-butylpyridine 26. Consider the phase diagram given below Liquid Q ‘Temperature > ~ A. A OB Composition At the intersection point Q the phases that are in equilibrium are {2Marks} {a} solid A, solid B and solid AB, (b) solid , solid AB, and liquid (0) solid 8, solid AB, and liquid (d) solid A, solid 8, solid AB, and liquid 27. Forthe titration ofa 10 mL (aq) solution of CaCO, 2 mL of 0,001 M Na,EDTA is required to reach the end point. The concentration of CaCO, (assume molecular weight of CaCO = 100) is [eMarks] (a) 510-4 g/mL (b) 2x10" gm (©) 5x10 git {@ 2x10 gmt4 | Chapterwise GATE Solved Papers Electrochemistry 28. At 298 K, the EMF of the cel!, Pt [H(1 bar)| H*Golution|| CI-|Hg,Cl, [Hg is 0.7530 V. The standard potential of the calomel electrode is 0.2802 V. Ifthe liquid junction potential is zero, the pH ofthe solution is [Marks] (a) 4.7 (b) 74 (© 80 @) 12.7 28. For the following reaction, 2MnO; + 5H,C,O, +6H* —» 2Mn?* +8H,0+10CO, °(MnOj /Mn2*) = +1.51V and E°(CO, /H,C,0,)=-049.V. At 298 K, the equilibrium constant is [Merk] (a) 10% (by 10°" (a) 10° Chemical Kinetics 30. -For a reaction involving two steps given below First step Gem 2H Second step G+H—>P ‘Assume thatthe first step attains equilibrium rapidly. The rate of formation of Pis proportional to {1 Mark] @id’ w®IG ©? Ga 31. Consider the reaction, Hy +C;H, —> C,Hg (© 10% The molecular diameters ofH,|andC,H, are 1.8 Aand 3.6 A respectively. The pre-exponential factor in the rate constant calculated using collision theory in mmol) s* ,i8 approximately (For this reaction at ao (SZ y Ng =1.11% 107m (mol)“'s“', where TH the symbols have their usual meanings) [2 Marks] (a) 2.5x10° (6) 25x10" (0 94x10" (@ 94x10” Chemical Thermodynamics 32. The molecular partition function of a system is given by v2 kg T)"?(8x3mkgT m= (SE , where the oe (z) r symbols have their usual meanings. The heat capacity at constant volume for this system is [Marks] fa) 38 {b) 6 {c) 9R/2 (d) 3R/2 Basics'of Organic Reaction Mechanism. 33. In the proton decoupled "C NMR spectrum of 7-norbornanone, the aumber of signals obtained is (1 Mark) @7 ®3 4. 5s 35. 36, 37. 38. GATE 2012 Identity the most probable product in the given reaction. (joss, a [1 Mark} 0 » hoo 09H ‘00H ) @ In the cyclization reaction given below, the most probable product formed is [1 Mark} Br y OH Ho 8 etc @ HOAG © Ox on © HOA) @ Cron The average length of atypical a-helix comprised of 10 amino acids is [1 Mark] (@10A () 15A )36A SAA Number of thymine residues in a 5000 kb DNA containing 23% guanine residues is [1 Mark] (a) 2.70 x10° (b) 2.70 x107 (€) 1.35 x10 (@) 1.35107 Shown below is a Hammett plot obtained for the reaction log ktAr-COCD o The change in slope of the plot indicates that [1 mark]eee ee eo oS (es) Peeeoeoaoeadcn eeoo GATE 2012 39. 40. a. 42. 48 45. (a) the reaction does nét follow linear free energy relationship (6) electrons are being withdrawn from the transition state in the mechanism (0) electrons are being donated tothe transition state in the mechanism (@ the mechanism of the reaction is changing The ratio of relative intensities of the two molecular ion peaks of methyl bromide (CHB) in the mass spectrum is [Mark (@) MP (M42 =1:3 (b) M* (M4 Qt =3:1 (2 MPM +2" (d) M™:(M + 2)" =1:2 A disaccharide that wil] not give Benedict's test and will not form osazone is [1 Merk) @) maltose (©) lactose (©) cellobiose (d) sucrose Choose the allowed transition [1 Mang ("Ep Es ) 'E5 925; ("ep ES (d) "Ey > "Ey The bond that gives the most intense band in the infrared spectrum for its stretching vibration is. {1 Mack] fa) C-H (6) N-H { O-H (d) SH An intermediate formed during the hydroformylation of olefins using Co,(CO} as catalyst is (Mark) (@) HCo(CO}, (&) H,Co(CO), (0) H,Co(CO), (d) HCo(CO}, From a carboxymethyl-cellulose column at pH 6.0, arginine, valine and glutamic acid will elute in the order [2 Marks} (a) arginine, valine, glutamic acid (b) arginine, glutamic acid, valine (6) glutamic acid, arginine, valine (d) glutamic acid, valine, arginine Identify the product from the following reaction. o (9-BBN = 9-Borabicyclo [33-1] nonane) Ci # @ Dm pp K 4 4 @ expctn Ls REN ed, “Tino, Nao Product teearks) on ; opp i Chemistry | 5 i 46. The product from the following reaction is, 47. Cat ‘ONO, ww + Product AO (2Marke} Coty Ho, HON, @ AO S HON. Cot kot Cat o 1 AO! CoHiz He NOH a > 8 3S ry CoHi7 @ Ac 8 NOH The acid catalyzed cyclization of S-ketodecan-t, 9-diol is given below - HO. SA hese ea oO Spiroketal (p-TSA = p-oluenesulphonic acid} The most predominant spiroketal is [2 Marks} ie » fr f “Y ta the reaction 9 0) wy OHO dct the product formed is [2Marks},6 | Chapterwise GATE Solved Papers GATE 2012 * " ‘Common Data for Questions 52 and 53, 9° Consider the 1 reaction ofte-amyl halides from the f ® L energy profile given below: ‘CHO 8G 49, In the reaction given below, identify the product ’ eye Cemesa THE se radu Pp 2.140 ‘0 3. sce CHyC10Mer, TSA, het foluenesulphonic acid; trahyclrofuran) (2 Marks} reaction \ 1 He Tor a C) LOCMeKOMe MooON ° 52. In the above reaction, X = Cl, Br or 1. Based on the graph, identify the alkyl halides (R-X) as Si, S2 and $3 @ O Reaction coordinate ie [2 Marks} my OMe R-Cl, $2 = R—Br and $3 S RU, $2 = R—Br and $3 R—Cl, S2=R—Vand S: OCMe(OMe},, RI, S2=. Common Data for Questions 50 and 51 53. Identify product P, and its yield relative to P, [2Marks) Consider the reaction shown below (a) Bis M and is the major product ots (b) Fis N and is the minor product. ‘OH (c) Bis N and is the major product CO 3 (d) P, is M and isthe minor product 7 = Pyridine + Statement for Linked Answer Questions 54 and 55 H ‘A 20491 cm laser line was used to excite oxygen TsCl= pioluenesiphonyl chloride molecules (made of °° Gonly| to obtain the rotational i Raman spectrum, The resulting rotational Raman 50, The oxidant X used in step 1 is [2 Marks} spectrum of oxygen molecule has the first Stokes line at fa) CO, 20479 cm" (b) 030, (co Nal 54, The rotational constant (usually denoted as 8) for the a ' oxygen molecule is [Marks] (d) mCPBA followed by NaOH Be eae 51, The product is (2 Marks) (©) 3.0cm™ (d) 6.0cm™ ° eee 55, The next rotational Stokes line is expected at [2 Marks} @ ro} (a) 20467 cm" (b) 20469 cm"! aaa A (0) 20471 cm (@) 20475 cm™ H 0 Bn General Aptitude a . 36. If (1.001) =3.52 and (1.001)? =7.85, then © oO 1.000" = [0 Mar H rm (a) 2.23 (b) 4.33 (c) 11.37 (d) 27.64ga20200009960-0- eeecece sc eoogooece GATE 2012 57. 58. 59. 60. 61. One of the parts (a,b,c, d)in the sentence given below contains an error. Which one of the following is incorrect? [1 Mark] | requested that he should be given the driving test today instead of tomorrow. {@) requeseed that (b) should be given (©) the driving test. (d) instead of tomorrow Which one of the following options is the closest in meaning to the word given below? 1 Markl Latitude (@) Eligibility (© Coercion (b) Freedom (d) Meticulousness Choose the most appropriate word from the options given below to complete the following sentence: Given the seriousness of the situation that he had to face, his__ was impressive. [tacky (@) beggary (0) nomenclature (0) jealousy {@) nonchalance Choose the most appropriate alternative from the options given below to complete the following sentence. IF the tired soldier wanted to lie down, he __ the mattress out on the balcony. TH Mark (a) should take (b) shall take (6 should have taken (d) will have taken One of the legacies of the Roman legions was discipline. In the legions, military law prevailed and discipline was brutal. Discipline on the battlefield kept units obedient, intact and fighting, even when the odds. and conditions were against them. [2 Marks} ‘Which one of the following statements best sums up the meaning ofthe above passage? {@) Through regimentation was the main reason for the efficiency of the Roman legions even in adverse circumstances (6) The legions were treated inhumanly as if the men were animals (9 Discipline was the armies’ inheritance from their seniors 62. 63. 64. 65. Chemistry | 7 (6) The harsh discipline to which the legions were subjected to led to the odds and conditions being against them AandB are fiends. They decide to meet between 1 pm and 2 pm on a given day. There is a.condition that whoever arrives first will not wait forthe other for more than 15 minutes. The probability that they will meet on that day is i 1 (ears) y 1 byt or oF ce a az OF The data given in the following table summarizes the monthly budget of an average household, [2aarks] Category | Amount @) Food | 4000 Clothing L 1200 Rent 2000 Savings | 1500 Other expenses 1800 The approximate percentage of the monthly budget not spent an savings is {a) 10% (b) 14% {c) 81% (d) 86% There are eight bags of rice looking alike, seven of which have equal weight and one is slightly heavier. The weighing balance is of unlimited capacity. Using this balance, the minimum number of weighings required to identify the heavier bag is (Marks) (a2 (b) 3 (4 id 8 Raju has 14 currency notes in his pocket consisting of only & 20 notes and & 10 notes. The total money value ofthe notes is % 230, The number of 10 notes that Raju has is [2Marks} f@ 5 (b) 6 9 (a) 10Answers with Explanations 1. (d) According to Heisenberg’s uncertainty principle, b Ay-dp, 2 yApy 2 where, Ay =uncertainty in position and Ap, = uncertainty in momentum Ay-Ap, 24 (: or 2. (©) Angular part of wave function, ie, Yim(@, 4) sin? Bcosbe?* We know that, (given) Oj i, Oys2 =e wet and m=+2 3. (@) Given, tx) = NOx? = ne"? For normalizable function, v= fyewde=t = [vet NPM at - 172 Nate 67% ~ axe ade =1 = NiGVa + VR - WR) =i te [7 ede = a} mal 4, {d)Since, the CO molecule is oriented along the z-axis, combination of 6, and, results in the formation of bonding orbitals while combination of either 6, and @, oF 6, and @ results in the formation of x bonding oil :. The wave function for rbonding molecular orbital = -) = ak +e8? 5. (b) General formula of spinel and inverse spinel is A™B}' OF. The main point of difference is that A?" fons Havea strong preference for the octahedral site and B* adopt the tetrahedral sites in inverse spinel structure. Such an arrangement is found inFe,O,( Fe** -Fe3'O,) ie, FeO, has inverse spinel structure. 6..(b) BF; has symmetrical structure (trigonal planar). That's why its net dipole moment is zero. NH, and ee has the pyramidal geometry as — ? a t é soot Ry fee tanto jnnscnied | NM RS at gS "nso neo ™ 7 Since, the direction of dipoles due to lone pair and due to bond is opposite in case of NF, its dipole ‘moment is less than that of NH, e 50, the order of polarity is ? BF, Point group. Given, 4C, axes LC, So, the point group is D,. a 8. (b) For a face centred cubic lattice, the Miller indices for the frst Bragg’s peak (smallest Bragg angle) are WM. 9. (a) CH,=CH—CH, Hy ES HFS Hs 653 Hay E52) Hy — S22 Has —fS2y Is E83) Hyz E832 Hy ~FS35, On putting values in the above matrix, we get a-E BO Bo a-E B 0 Bp a-EcS e © e Gc 6 eC 6 e GATE 2012 . : Chemistry | 9 Note Inasecular determinant, (j)all diagonal eleménts aE CH Gi) off-diagonal elements between atoms ii) all other elements = 0. Crossineed sone + 12, (d)K,C1,0, + 4NaCl+ 6H,S0, —> 2C10,Cl, ted pce i o + 2KHSO, + 4NaHSO, + 3H,0 < :CHO,Cl, + 2NGOH— NaC, + HCI yellow sltion Na,CrO, + 2AgNO, —> Ag,CrO, + NANO, redo te 13. (d) Al™ form chelate with trifluoroacetylacetone which is used for the separation and quantitative analysis of aluminium ion by gas chromatography. 14, (4) The electronic configuration of the given ions is as ° Ca 2152, 22, 208, 38, 39° Mn2* = 152, 257, 2p®, 35%, 3p8, 3d oli) Zn =15?, 25?, Ip® 3s, 3p°, 3d" Thus, the size of Zn’* ion is smallest and of Ca is x 10) é largest among the three due to increase in effective 1 x O]a0 aauclear charge with increase in atomic number. lo. x Smaller the size of ion, higher is the hydration enthalpy. Thus, the order of hydration enthalpy is Zn > Mnt* > Cat (2047 not” adie)” a577e 9") ‘On putting the value of x in eq. (), we get 15. fe} The structure of Fe,(CO), isas E=a+V76,0,0-V28 i i oc. 11. ©) Monoalky! tichlotoslane on hydrolysis. gives a Bes complex crosslinked silicone polymer. Kt OH oc Neo L CH,SICL, + HO — Rea aee Thus, it contains 6 terminal and 3 bridging carbonyl Gn groups. chy chy cH, 16. (c) The magnetic susceptibility of a paramagnetic substance pax. Would decrease with increase in HO—S-OH+ HO—S—OH + HO—R-OH temperature. The variation of Xpu With bu bu a temperature is given as CH, CH, CH, =H, 2HO—-Si_O—Si-O—$i_OH On On OH (where, C = Curie constant)10 | Chapterwise GATE Solved Papers Thus, the plot of y7 versus Tis ww = 17. (b) InNa[PCl} let the oxidation state of P is x tt E16 x5 5 The IUPAC name of Na[PCl,] is sodium hhexachlorophosphate(V). 18. (@) In all the reaction, one of the reactant is ICr(H,0),]?* which is a very labile complex ion and can easily lose a water molecule. It acts as a reducing agent ‘Among the other reactants, [Col(NH,}5]°* is the most reactive as | is capable of forming a bridge with the reductant leading to the formation of the intermediate bridge complex. Slow ICoKNHs)31** + [Ct O}g]* > [(H,0) ,Cr—1Co(NHy) <1" [(H,0}Cr-Co(NH)5]"* eso, [Cr(H,0) 11?* + [Co(NH,),(H,0)]"%, Note The above reaction involves inner 19, (b) The extent of Mossbauer quadrupole spiting varies inversely with the number of unpaired electrons, so the order of splitting is K, Fe(CN) ,(NO}] > FeCl, -4H,0 > FeCl, -6H,0 Unpairede” 0 4 5 AE, 176mm 0.300 mms 0.02 mus 20, (a) Oxygenated haemoglobin [Hb(O, }4]is diamagnetic in nature, so there are following three posibilities about the nature of Fe andO, (Low spin Fe* + Singlet O —> diamagnetic anapretc(damagreio (i) Low spin Fe* inpsiedlecton) + OQ} + Antiferromagnetic ally diamagnetic sepia) (iid Lowspin Fe* + OF — —> diamagnetic (Gamage) (shamappetic ut of these (i) resembles to be option (a) GATE 2012 21, (b)Co* = [A307 In octahedral field th HAE Tg fiom Orgel digh In tetrahedral field tet Ht 4Aq (from Orgel dig) 22, (c) The formula of Zeise's salt isKIPICI,(C,H,)]-H,0. Let the oxidation state of Ptis x. KIPICI(C3H,)IH,0 #14x+(-0x34040=0 tHtx-3=0 2 xe Pra42 ‘The structure of Zeise’s salt is (Normal C=C length = 1.34 A) 23, (a) The possible isomers of (NH) ,M(CN),] are HitlenrnnngON Hh SN ae Hy SEN NEL NH ison ‘ransionn \, Thu the number of possible isomers is 2. sphete\24. (b) Chemical potentials of A in two phases are given as, mechanism, * WG) =H) + RT oxy wals)- wy On differentiating both sides with respect 10 T, we get dinx, — 1dldyG/7) igge Riese, Sgt Rr? ‘On multiplying both sides by d7 and integrating from xq =MWlnx, =0)t0 x4, we get ints 1t AgH J dinx, J, rar 1 -3 (ong tH =D| GATE 2012 Chemistry | 11 © 45, (a Thebasein which lone pairs are more avilable for The half-cell reactions are 7 donation, forms most stable adduct with the Lewis H, 9 2H «2 € acid, B(CH). Hg?! + 26°” — Hg eG Presence of electron releasing groups like Me, Hy + Hg3’ — 2H +Hg : makes the e~ more available for donation, whereas Net cell reaction an electron withdrawing group decreases the cos, © electron releasing tendency of the base. Egg = Egg = Mog 6 ren a THE? IPa, hes, Qj forms the most stable adduct with Since, the liquid junction potential is zero, Ce Ky BICHs)s- eS LA and Le are crowded molecules N SNS s0 do not form adduct with om e Lewis acids. 07530 ~0.2802= 257™*7 1 ogiy*y) 26. (0) At point Q, solid AB,, solid 8 and liquid are in e equilibrium. g 29. (b) 2MnO; + 5H,C,0, + 6H" > 2Mn”* +4 8H,0 i +10C0, E 5 bigs Given, Ey oc yyze =1SIV € a She, and Ei oY Lae Solid. AB, as e ad 7 sod Fc =F catade ~ E ade a Sold AB, Compostion 2 51-(-0.49) 6 + Sols a = : The half-cell reactions are: © 27. (6) Na, EDTA + CaCO, —> CaEDTA + 2Na a N,V, (CaCO) = NzV; (Na, EDTA) [2C0, + 28° —+C,07F]x5 eG N, x10 = 2x0,002N So, the balanced equation is ¢: For NajEDTA, 1N= 2M} 2MnOj + 5C,07° +6H* —> 2Mn** +10CO,, CS 4x10? a +8H,0 Tw and number of electrons involved, » = 70 os , At 296 K, © Molarity = Normality (ForCaco,) « 0.0591V & 2 Eg OK 0s91v e : 39 BK =2x10-4 molt lope, 2210 = 22107 100 i, 0.0551 7000 - 0, e = 2x10" giml : 00551 28. (Egy = 0.7530 V antilog 338 = 107 6 * 2 o2802v 30. (4) For first step, al i? © : x, = Feat = Festade ~ Ecode G e 0.2802 - 0 =02802V THY = Ket) ; or (HI =KY ICT ati12 | Chapterwise GATE Solved Papers For second step, a Pl _ py Rate of formation of P = ST = k GH On putting the value of [H1] from eq, (, we get DP) _ pvr v2 a Ke “MIGlIGl __= KG? Eek’ = KY KL Wl gn dt 31. (a) Pre-exponential factor (from collision theory), 2 Az (2) Ng mH where, 6 = collision cross-section = nd? and d=i0, +dg) > 34. et = leas d= 0.8 43.6)=564)=27 = nd? =314 x (2.7)(A2}? = 22.9 (A2)? = 22.9 x10 m? 2 and) Ne ™ = 22.9 x1.11x10" x10 m(mot')s* =2.5x10° m? mol Ph—O—O" HCH HQ ect "© Cy noo Cen opal stent @ re HyC-—CHy HyC—C—-CH, i }) tO fe \ camenehioperoside feeradea o-0" 9-0H G | I HyC-C—CHy HyC-CHHCH; _HyC—C—CH é a 5 7 = Ee S ype & ‘psi Hyc-C—cH, ©© cane : @ a0 a e Ho“ | © ¥ te = oS eo AH © i srl Cycisaion —_Yetaton -Br <9 Ho? 4 e notes nents ot anion sable oat) vo ou mentee 6 Thus, the product ofthe reaction is 20 HOY 36. (b) In cc-helix structure, 3.6 amino acids are present iit ‘one turn, covering 2 distance of 5.44, i 1x10 10 amino acids will be present in =~" turns and & 5 Pe the average length of achelix containing 10 amino & acids | EXO x54 Isa 37. (c) NDNA, A always binds with T and C always binds with G (where, A = adenine, T = thymine, C = cytosine and G= Guanine), e., A=TandC=G and A% + T% + C% + G% = 100 i Given, i = 23% = C%and A% = T% = x oS ce X86 + 6 + 2386+ 23% = 100% 2x =100 ~ 46 2x = 54% 27% Thus, number of thymine residue = 27% of 5000 kb =22 5000 x10"b 100 =2.7x5x105 213.5109 31.35 10° 38. (d) Hammett plot is typically linear with either a positive or negative slop. Non-lineatity in the Hammett plot shows that 2 substituent affects the rate of reaction or changes the rate determining step (F reaction mechanism of the reaction. 39. (c) The abundance of the two isotopes of bromine is, almost equal ie.,”*Br(50.69%) and "Br{49.31%) ' Hence, the mass spectrum of methyl bromide shows two very intense peaks of roughly equal Chemistry { 13 intensity at m/z 94 and 96 Which are the M** and M" peaks. +— (no change, hence does rot appear in the mass specu) 40, (d) The monomer units of sucrose are glucose and fructose, which are joined together at the hemniacetal of glucose unit and hemiketal of fructose. The bond formed (ether bond) is called slycosidic linkage. Since, there is no hemiacetals remaining in the sucrose, itisa non-reducing sugar, ie’, does notréduce Benedict's solution, Moreover, it does not form osazone due to the absence of free aldehyde or keto group, which are necessary to form osazone. HOH mot HOC 0. fl HOH t HOH rem linkage 41, (} For the electronic transition, the selection rule are 1. Multiplicity remains the same, ie. AS = 0 2. Components of total orbital angular momentum along intermuclearaxis, A a =0, 41 3. For equal nuclear charges, 2} <3 Ef or 2 <> 2B transitions are allowed, Thus, 'Z} <> "E) transition is allowed as AS=0 Aa=0 Zp sx 42. (IMIR spectrum, polarity of a bond «intensity ‘Among the given bonds, O—H bond being most polar gives the most intense band in the infrared spectrum for its stretching vibration. 43. (d) In hydroformylation reaction, first of all catalyst Co;(CO), undergoes hydrogenation to give the acidic hydride HCo(CO),, which can also be prepared directly14 | Chapterwise GATE Solved Papers GATE 2012 Co,(CO}, + Hy —> 2HCo(CO), 47. (a) imernde HOAA AA piste CH=CH, ‘ yo (CO) = - HC0(CO}, + RCH=CHp > F-CotCO), : ecbiakt @ swanomeic eee AL Roo AX 48 (a) —CHO group is more reactive than C=O. = “0 ° Co(CO, ——* + oxCOly 44, (d) The iso-elecric point of arginine, glutamic acid and & valine is 11.15, 3.22 and 5.96 respectively. Thus, the order of elution of these is (from a carboxymethyl-cellulose column at pH 6.0) glutamic acid, valine, arginine. 45. (a) 9-BBN adds to the less substituted site and H atom ‘occupy a position cis to —OH. So, the product of the reaction is 49. @) 1 @ PR “ a 20 OWE re © oi 4 3 excess CHyCIOMel, SA, eat 46. @) CH) —CHMGB os Ge Ge TF ie Z e . Bees CCM: @ sho ‘OMe tw OH not 5 a Coty eM vo Nowe @ ONG Oy No T ‘7 & — 50, (b} Since, the syn addition takes place, the reagent must be Os0,, rel ° Nivoso compound le yt on Cotay YY iP Ho, —=— © HONS 7 waning \ A _ Rearangement t 4 7 il XK & e@ bu OK OH CO KA Product The above reaction is an example of Barton reaction, a photochemical rearrangement.@©_O— e © © © © e © 6 6 6 e ) 6 e © © © 6 e GATE 2012 52. (b) We know that the order of reactivity alkyl halide is, R-1>R-Br> RCI and Reactivity = energy stability The order of energy is $,> 5, > Sy Thus, 5, =, S; 53. (a Lyx Histon 4) Brand S, = R—Cl 2 Aan eA NY ul Q Ainorgadact ne sabe essakh cong Space, uve ‘The order of energy is P, > Py So, P, is M (less stable, So has more energy) and is the minor product. 54. (b) For rotational Raman spectrum, AE =B(4j +6) Forte fis fine, j=0= AE =68 AE = 20491-20479 6B =12 B=2cm™ 55. (c] Forsecond line, j =1 AE = BAX 146) = 10B =10 x 2.0 = 20cm «Second rotational line is at 20491- 20 = 20471cm™ 56. (d) Let 1.001= x x75 53.52, x08 = 785 (2 19 062 =3.52x 7.85 = 2764 57. () 58. (b) The meaning of Latitude is Freedom. 59. (dj Given the seriousness ofthe situation that he had to face, his nonchalance was impressive Chemistry | 15 (6) If the tired soldier wanted to lie down, he should have taken the mattress out on the balcony. . (a) 2. (C}OBis the fine when both A andB arrive at same time, Total sample space = 60 x 60 = 3600 Favourable cases = Area of OABC ~ 2(Area of SRC) =3600 = 2x ($345 x 45) =1575 1575 _ 7 Henc: 1d probability = 1275. = 7 <, required probability = 7 = 7 (6) Total budget amount = 4900 +1200 + 2000 +1500 +1800 = 710500 Except savings, other expenditure = & (10500 1500) =% 9000 Hence, required percentage = 2000x100 10500 86% (2) Suppose category of bags are as follows Ay Aa Ay BB2Bs GCr Ist weighting A vs B CaselA,A,A; = B,B)B, A\AgAy # 8,B28, «Either C, oC; is heavier. Either A or B would be heavier (say A > 8) 2nd weighting G¥sCy; fC > C;, then, HFG Ay, then A, (2) Suppose the number of € 20 notes = x Case It and the number of € 10 notes = y According to the question, 20x +19y = 230 and key=l4 iy From Eqs. (i) and (i). we get x=9 and y=5 Number of € 10 notes = 5g-6-8-— Atomic Structure Syllabus ‘Atomic Structure Quantum Theory: Principles and techniques, applications toa pattice in a box, harmonic osciator, Tigid rotor and hydrogen atom. Approximate technique : Variation and perturbation. Rotational, vibrational, electronic, NMR and ESR spectroscopy. iu GATE 2011 (1 Mark Questions) ¥ Solution Points 1. The region of electromagnetic spectrum employed in the electron spin resonance (ESR) spectroscopy is (a) radiowave (b) microwave (c) infrared {d) visible GATE 2010 2 2. The wave function fora harmonicoscillator described by Nxexp| (- ~| has (@) one maximum only {b) one maximum, ofe minimum only _ {) two maxima, one minimum only (@) two maxima, two minima only 3. An electron of mass mis confined to a one-dimensional box of length b. fit makes a radiative transition from second excited state to the ground stale, the fequency ofthe photon ete is 9 3h @ O . ano? amb? 2h ao wb? ” eb? GATE 2009 4, The de-Broglie wavelength fora Heatom travelling at 1000m/s (typical speed at room temperature) is @) 99.710"? m (b) 199.4 x10"? m (©) 199.4107" m (d) 99 x10 m2 | Chapterwise GATE Solved Papers Atomic Structure GATE 2005 , ¥ Solution Points 5. The vibrational partition function for a molecule which can be described as a * simple harmonic oscillator with fundamental frequency v is given by vos) wf-t tl onfilemtsy e emit Ca 6. The 2s-orbital of H-atom has a radial node at 2ag because W , is proportional to @ é +t ® @ + ra 2* a5 % aoe d) \2-—— ® ( J ‘i ‘ fe i) 7. The function e+” (a > 0} fs not an acceptable wave function for bound system because © @j_ itis not continuous (b) itis multi-valued su {c) itis not normalizable (d) All of these 8. The set of eigen tunons sin 0 £25 a.0=42,3 aa {a) orthogonal (b) normalized (6) both orthogonal and narmatized (d) unnormatized GATE 2004 9. Which one of the fotlowing is not a photodetector? e (a) Bolometer (b) Charge-transfer device - fc) Photomultiptier tube @ Silicon diode & 2 10, tnunits ot, the energy difference between fevels corresponding to 3 and ami’ 2 node eigen functions for a particle of mass ‘rin a one-dimensional box of. length tis (at h) 3 os a7 GATE 2002 5 & 11, The velocity of the electron injthe hydrogen acom ~ (a) increases with increasing principal quantum number . (b) decreases with increasing principal quantum number P (c) is uniform for any value of the principal quantum number 4d) first increases and then decreases with principal quantum number \29 © O_ 99000000 6 e 6 e 9 e ° é e Atomic Structure GATE 2001 12. As per the uncertainty principle, Ax- Ap equals to at “ot mn 2 ms or. (d) z0r0 GATE 2011 (2 Marks Questions) 13. The wave function for @ quantum mechanical particle in a one-dimensional box of length ais given by y = Asin =. The value of A for a box of length 200 a nin is (@) 4x 10% (amy? tb) 10V2 (amy"? (©) ¥2N0 (nim? (@) 0.1(0m)- ‘Common Data for Questions 14 and 15 ‘Atyypothetical molecule X¥ has the following properties: Reduced mass = 2 x 107kg XY bond length = 100 pm Force constant of the bond =8 x 10?N/m ‘ 14. The frequency of radiation fin cm“ units) required to vibrationally excite the molecule from v = 0 to v = Istate is (@) 31848 (b) 2123.2 (1061.6 (@) 840.0 15, The frequency of radiation (in em" molecule from J = 0to J = 1state &s @ 14 ) 28 (©) 32 (d) 3.6 GATE 2008 Common Data for Questions 16 to 18 Aneeectron accelerated through a potential difference of volt impinges on a nickel surface, whose (100) planes have a spacing d = 351.5 x10"? m Units) required to rotationally excite the (351.8 pm). « 16. The de-Broglie wavelength ofthe electron is A/pm = (a/@)". The value of a in voltis . @ 15x10" vce fb) 1.521058 (6) 6.63x10% (@ 2.5 x10- 17. The condition for observing difraction from the nickel surface is fa) .>> 2d (b) As 2d (Asad (0) 22 ad 18. The minimum value of volt) for the electron to diffract from the (100) plaries is . (a) 3000 (b) 300 © 30 @) 3 : we Chemistry | 3 v Solution Points+ | Chapterwise GATE Solved Papers 19. Aparticle is confined to a one-dimensional box of length 1 mm. Ifthe length is changed by 10° m, the % change in the ground state energy is, @ 2x10% (b) 2x107 (© 2x107 0 SATE 2007 20. Consider a particle of mass m moving in a one-dimensional box under the potential V = 0 for < x< aand V = « outside the box. When the particle is nits lowest energy state, the average momentum (< p, >) of the particle is @) =0 O =2 A h o ane (0 =7 21. The uncertainty in the momentum (4p) of the particle in its lowest energy states fa) bp, =0 (0 dpe a GATE 2006 22. The zero-point energy of the vibration of °Cl, mimicking a harmonic oscillator with a force constant k = 2293.8 Nim is (@) 10.5107" J (0) 148 x10") (© 209x107" (@) 206x107" 23, Which ofthe following paits of operators commute? d dd? 2d @) xand 7 Oo Gand at 2 © ona @e ana GATE 2005 24, First order perturbation correction A €\? to energy level €, of a simple harmonic oscillator due to the anharmonicity perturbation 7 x° is given by @Aep=y b) Ae =y? (deat d) Aes GATE 2000 25, The system for which energy (6) increases quadratically with the quantum number (n} (@) particle in a one-dimensional box (6) hydrogen atom. (6) one-dimensional harmonic oscillator ) tigid rotor Atomic Structure ¥ Solution PointsAnswers with Explanations 1. (b) Electron Spin Resonance (ESR) isa type of magnetic resonance. In it, the sample is loaded into a high frequency resonant cavity ina slowly varying uniform magnetic field. Unpaired electrons irradiated with microwave radiation ata fixed frequency will undergo resonant transition between the spin up and spin down state ata characteristic magnetic field. 2 Ory =Neexp = On differentiating, we get oy 2 ax? ax ret 2) ao( #2) 22) Zea Putting x (On further differentiating, 2 2) St eneo(-2] (-2ar + (1 ax?) ar _it on(- =Nexp- Ba - Va) -t =Nexp ? [2a] > 0 (minima) Atce4 1 =Nexp ?[-3Va + Val 4 =~ Nexp ? [2a] < 0 (maxima) Hence, the given wave function has one maxima and cone minima only. Since, E = hy, length is b, and for ground staten, = tand for second excited state ny =3 On putting these values, we get 1? - a7} 8mb? O-Dh_bh_ © 8mb? ~ &mb? he * mb? bv= (a) = my 6.63 x10™ © 41.66 «107% x 1000 = 99.8 x10"? m . (b) Vibrational partition function fb)6 | Chapterwise GATE Solved Papers Atomic Structure 1 yf 6.0 va=—=(2] [2 Oo als] ( Atnode, va, =0 zu a0 Thus, the function is orthonormal, i.e, orthogonal as well as normalized Alternate method Conditions for orthonormality are w= yj yj) de= Oat Fj =1ifi In the given function, i= jand Thus, Va [ - 7 Thus, the given function is orthonormal 0 9. (a) Photodetectors are used primarily as an optical receiver to convert light into electricity. They work on the principle of photoelectric effect. Photodiodes (Ge-As diode, Si diode), photomultiplier tube and charge transfer device (mainly charge coupled device). Bolometer, on the other hand, is a device used for measuring the power of incident EMR via the heating of material with a temperaturedependent electrical For normalizable function, resistance, =Jy-wdr=t . ve few 10, (0) The energy difference is in betweenn=3andn=2 d= fe™ node be the particle losing energy. For particle in one-dimensional box, E pat ni=m) s, ‘8ml? € Thus, itis not a normalizable function. 52 P18? - 27) ee Further, the given function is non-continuous. 8m? 2 ome 2 fm ae 8.10 ya sin amit For orthonormal function, Energy difference is 5 in units of viv deat (2. nm (2. nex 11. (b) Velocity decreases with increase in principal wot = [fain alg ak quantum number as & = fa sint(™) dc Velocity of electron v = Z af a “ af [i cos 2 bs 12, (b) According to Hesenbes uncertainty prince @ a a Ax dp? (: ns ) mei] ; * @ " . ail 13. (d) Given, isin? Wave function y= A sin =)? ae : @ a 2nn In order for the functions to be normalized, ‘We must have & Jpvrde=a? sin? (2)eeoaoo0oecgngogn0o0odo@ 30009 Q @oeceoecoco Atomic Structure m Let Bac, Fde=ac aa 2 Then, [y'de= Asa r sin? CdC 0 2 Many 2 = 0.1m)? 14, (€) The frequency ofthe molecule XY in wave number units is 2106157110" =1061.6 cm” 4 to, = 1061.6 -0 }061.6 cm” G+ n? 15, (b) Ey = Fi When j =0, E,=0 g Gann a Me pA? jaa 20 © ur? pr i eae We know that Chemistry | 7 any? -c = 6.6.x 107% 4x 8.14? x 2 x 107 x (100 x 10)? x3 x 108 7 6.6 x10 “4x 9.86 x6x10" x10 6x10" © 24x107% = 278.9 m" mt 16. (ak =— or v A 2x 9.1x107" x1.6 x10" x@ rR © 2X 91x10" X1.6%1 _ (6.6 x10)? “x 9.1K10 X16 x10? 356 x 10° © 32x 91x10 49 x10" = 1.5 x10V 17, (b) Brage’s equation is m 2d nk =2dsin8 or sind For diffraction, sin8 <1 For first order difraction,n a ssl 2d Asad8 | Chapterwise GATE Solved Papers 18. (d) For minimum value of 6, 4 must be maximum. 1. is maximum, when si ie, mh =2d sin = 2d mead For firs order diffraction, n= 1 a d=2d rele é Given, 1.5 «10° 4x 351.8 x10")? 2x107 100 10 =2x107 x10% =2x104 20. (a) The average value of the linear momentum along the x-axis is an)" San(®) x a)idx a 20 al) oo( 2} aye ay Ma The integral on the right is zero (as sine function is symmetric and cosine function is antisymmetric around the centre of the range). So, we conclude that the average linear momentum is zero, 21. (b) The momentum ofthe particle can be in the positive and negative directions and Gertainty is from 0 to a. Atomic Structure Thus, uncertainty in momentum, ah Hin=4 22. (b) Reduced mass 35 x107 x 35 x 107 (kg / mol)? © 85x10" +35 x 107) kg/ mol (6.023 x10” mol!) 1.225 x10? SRT & 70 x10 x 6.023 x10 & =2.9x107% kg x Zero point energy * ho 23.14 \2.9x10% 6.6 x10 x 2.81x 10 6.28 S 476x107" J = 1.4766 x 107% 23, (b} Two operators commute ifthe following equation is true (i= At-EA-0 - d nd (a) xa Fe Reto =x-2 fy =x-1"09 a A fia =. xf09 = fa xt'00 ie ~21A, B= IE Al, so these operators do not commute. a_d ed? ad (b) A= —, 24st Win Sandie SS «28 Ac d[d? 2d AEf() = —|—_ fl fo fea ( @ 2d? = foxy +4 $i + 29 = 170) + 28"9Atontic Structure 2 @-0-0- ieet2di| Ed at x) < {09 @ 2d) a at 4) £0 2d, P +e =f") +260) GA-A8 1. These operators commute, a de” ik ® Leo Similarly, x Cen & a2eocoe Sinice, H’ is odd ie.,x°, the E' will be zero, & @ C6 6 © © a S Cc cS é e e e e 2 and 4 do not commute. 24, (d) First order correction to the ground state energy is [eH = 18) Chemistry | 9 25.(@) The lowest possible energy for paricle in one-dimensional box = 8 ma? Forn=2, itis 2h &ma? Ah? ie, 4 8ma' Thus, it increases quadratically. The energy levels ofthe quantum harmonic oscillator is he (n + j)r0 2 Here, energy does not increase quadratically with the quantum number.Chemical Bonding and Molecular Structures Syllabus Chemical Bonding and Molecular Structures Valence band and molecular orbital theories. Huckel approximation : symmetry, point groups. Crystal systems and lattice, Miller planes, crystal packing. crystal defects, Bragg's law, ionic crystals, band theory, metals and semiconductors, different structure of AX, AX, ABX, compounds, spinels. GATE 2011 (1 Mark Questions) 1, The band structure in an n-type semiconductor is i & @t GATE 2010 2. Band theory predicts that magnesium is an insulator. However, in practice it acts as a conductor due to ia) presence of filed 3s- orbital (b) overlap of filled 2p and filled 3s - orbital (©) overlap of filled 3s and empty 3p - orbital (4) presence of unfilled 3p - orbital GATE 2009 3. The geometry around the central atom in Cl" is (a) square planar (b) square pyramidal (0 octahedral (d) trigonal bipyramidal y Solution Points e €Chemical Bonding and Molecular Structures Chemistry | 11 8 4. The coordination number of the Ba2* ions in barium fluoride és 8. The ¥ Solution Points coordination number ofthe fluoride fon is e @s ws 1 @2 5. Among the following, the isoelectronic and isostructural pair is Se (@) CO, and SO, (b) $05 and 5e0, © (o) NO} and TeO, (d) SiO and POF © GATE 2008 6. The highest occupied molecular orbital of HF is © ‘al bonding (b) ant-bonding (©) ionic (@) non-bonding OS athe point group of NSF is 6 (2) Dag tb) Cay (0 Dy @ Gy 8. Among the compounds Fe,O,, NiFe,O, and MnO, {@) Nifez0, and MnO, are normal spinels (b) FeO, and MnO, are normal spinels de} Fj, and MnO, ate inverse spinels {@) FeO, and Nife,0, are inverse spinels & 9. NaCl is crystallized by slow evaporation of its aqueous solution at room | temperature, The correct statement is (@) the crystals will be non-stoichiometric {b) the crystals should have Frenkel defects (0 the percentage of defects in the crystals will depend on the concentration of the solution and its rate of evaporation (4) the nature of defects will depend upon the concentration of the solution and its rate of evaporation 10. CaTiO, has a perovskite crystal structure, The coordination number of titanium in CaTiOs is @9 6 @3 (a) 12 } GATE 2007 > 11. The ground state term for V3" ion is (a) F (b) 2F 6 fo? (@ 20 © GATE 2006 Se 12. The symmetry elements that are present in BF, are {@) C5, yp, 3Cy (b) G,,3C,, 5,6, 6 (Cy, 3Cz, 6p, Sp 1) G04, 54,1 © GATE 2005 6 13. The shape of the molecule XeO,F, i (a) distorted tetrahedral {b) square planar e (0 Wwigonal bipyramidal (@) tetrahedral12 | Chapterwise GATE Solved Papers GATE 2004 14, The structure of SF, is (@) octahedral (© trigonal bipyramidal 15, The bond angle of ClO is {@) smaller than of f,0 (0 smaller than that of HzO (b) tetrahedral (@) square planar (b) greater than that of HO (@) same as that of F;O Chemical Bonding and Molecular Structures 16, On the basis of LCAO-MO theory, the magnetic characteristics of N and N3 are {@) both diamagnetic {b) both paramagnetic (No diamagnetic and N3 paramagnetic (@) N, paramagnetic and N} diamagnetic GATE 2003 17, According to MO theory for the atomic species C {a) bond order is zero and itis paramagnet (6) bond order is zero and itis diamagneti (0, bond order is two and itis paramagnetic (d) bond order is two and it is diamagnetic GATE 2002 18, Which of the following species has two nonbonded electron pairs on the central ator? (a) TeCl, (oC old, (@) Pcl, 19. The species which has a square planar structure is . (a) BF (b) FeCl, (0 Sy (@) XeF, GATE 2001 20, Icosahedral structure is generally exhibited by ac (b) Si () Ge @B 21, The hybrid orbitals used by bromine atom in BrF, are (a) sp? ) sp* (0 pd @ spd? 22, The symmetry point group of the BF, molecule is @ Gy (0) Dy, (0 Cy (@ Day GATE 2000 23. Which of the following statements about the molecule NOC is correct? fa) thas a linear structure {b) It belongs to the point group C, (©) Itdoes not have a dipole moment (d) It isa chiral molecule y Solution Points1900008090 9H 0. © © 6 6 © e e Chemical Bonding and Molecular Structures 24, Among the following mélecules, the shortest bond length is to be found in fa) C (b) Ny (9 O, @h GATE 2011 (2 Marks Questions) 25, According to VSEPR theory, the shapes of [SF,Ci]* and [$,0,]" should be a) trigonal planar for[S,0,]" and trigonal pyramidal for {SF,Cl}* (6) both trigonal planar (©) ‘tigonal pyramidal for[S,04]?" and trigonal planar for [SFCI)* (@) both trigonal pyramidal GATE 2010 26. According to VSEPR model, the shape of keOR,T is, {@) octahedral (b) trigonal bipyramidal 0) square pyramidal (€) pentagonal monopyramidal 27. The point group of CIF, molecule and its comesponding number of irreducible representations are respectively (@) Coy and 4 fb) Cz, and 4 (0 Gy and 3 () Cy and 3 28, Fe,O, and Co; are metal oxides having spinel structure, Considering their CCFSFs, the correct statement regarding their structure is {@) both have normal spinel structure {b) both have inverse spinel structure {0 Fe,Q, has normal and Co,O, has inverse spinel structure (€) FeO, has inverse and CoO, has normat spinel structure GATE 2007 29, The pair of compounds having the same hybridization for the central atom is (@) Xef, and [Sify] (0) INCI}? and {Pel (1 NiCO), and XeO,F, (@ [CoINH,),]* and (CotHt,0),1* Common Data for Questions 30 to 32 trans, 1, 2 difluoro ethylene molecule has a 2-fld rotational axis and an inversion centre 30. The number of distinct symmetry operations that can be performed on the mofecule is @2 4 6 @8 31. The untber of irreducible representations of the point group of the molecule is @1 (b) 2 3 @a 32. two H atoms ofthe above molecule are also replaced by F atoms, the point group of the resultant mofecule will be @ C, ©) Cy cy @) Day Chemistey | 13 ¥ Solution Points14 | Chapterwise GATE Solved Papers Chemical Bonding and Molecular Structures GATE 2006 33. The atomic radius (in em) of an element with a body centred cubic unit cell of volume 75.8 cm? mol, molecular weight 137.3 and density 3.62 g cm” is @ 15x 10% 16 x 10% (@ 2.0 x 10° (d) 2.2 x 10% 134. (KeOg]* is octahedral whereas Xef, isa disordered one, because (a) fluorine is more electronegative than oxygen (b) Xe has a lone pair in Xef, (0) Xef;, is neutral whereas [XeOg]* is anionic () Xe—F bond has more ionic characters, 35. The arrangement of sulphur in zinc blende and wurtzite structures, respectively are () hexagonal close packing and cubic close packing (0) cubic close packing and hexagonal close packing (simple cubic packing in both the structures (d) hexagonal close packing in both the structures 36. The crystal structure of PbO, contains (@) octahedral and tetrahedral units (©) only octahedral units (© octahedral and pyramidal units (@) octahedral and square planar units 37. Ifthe dipole moment of HCl is 1.08 D and the bond distance is 1.27 A, the partial charge on hydrogen and chlorine, respectively are (a) +1.0 and -1.0 (6) +0.85 and -0.85 (@) +0.356 and -0,356 {d) +0.178 and -0.178 GATE 2005 '38. The incorrect statement for solid sodium chloride is that {@) both sodium and chloride ions adopt inert gas configuration 4B} the conduction band is full (©) the conduction band is empty (@) the valence band is full GATE 2004 39. The structures of N(CHy); and N(SiH), respectively are (2) trigonal planar and pyramidal (b) pyramidal and trigonal planar (©) pyramidal and pyramidal (€\ trigonal planar and trigonal planar 40. The ground state term symbols for high spin d's" and d® configurations, respectively are (a *Sand Ss (b) °P and 3s (© 7Sand °s (d) 7P and °s ¥ Solution Points@6-® 0 -0-0-2-0-9 ©-@. 0.8 0.0-9 6 © © © e 6 6 e Chemical Bonding and Molecular Structures 41. The spinels CoFe,O, arid FeFe,O, respectively are {@) inverse and inverse (b) inverse and normal (0) normal and normal (@) normal and inverse GATE 2003 42. The number of manganese ions in tetrahedral and octahedral sites, respectively in MnO, are (@) one Mn®* and two Mn? (6) one Mn™ and two Mo™ (©) twoMn® and one Mn (@) two Min” and one Mn* 43. The xenon compounds that are isostructural with IBr; and BrO3 respectively are (a) linear XeF, and pyramidal XeO, (b) bent XeF, and pyramidat XeO, (6) bent XeF, and planar XeO, (@) linear XeF, and tetrahedral XeO, GATE 2002 44, The structures of O} and Nj are (@) linear and bent respectively (b) both linear (0 both bent 4) bent and linear respectively 45. Sodium metal crystallizes in the body centred cubic lattice with cell edge a. The radius of the sodium atom is (@) alv2 () ay3/2 (©) av3/4 @ al2v2 46. The bond order for N, 2,3, 03 varies as (Nz > Nz > 02> 0; Np > 0, > Nz > OF (4.0, >N,>0;>N; @NZ>N, > 0; > 0, GATE 2000 47. The compound (SiH) Nis expected to be {a} pyramidal and more basic than (CH,)N (b) planar and less basic than (CH,)5N (©) pyramidal and less basic than (CH,),N (@) planar and more basic than (CH,)N Chemistry | 15 y Solution PointsAnswers with Explanations 4, (a) The band structure in an n-type semiconductors as Energy: This is because a large energy difference (gap) exist between valence band and conduction band in case of ‘a semiconductor and addition of an impurity (having higher valency) results in the n-type semiconductor, Thus, [represents the n-type semiconductor. 2. () The electronic configuration of Mg is. 1s, 2s?, 2p®, 35%, 3p? In it 35- orbital is completely filled and 3p-orbital is empty, There is very small energy difference between 3sand 3p- orbitals, Thus, they overlap and make the Mg a conductor. | conten band ap Be 8} BE S| 3. (d) CIF has 34 valence electrons. Cl has 4 bonding paité around it and 1 non-bonding pairis also present. If all 5 groups of electrons were involved in bonding, the shape would be trigonal bipyramidal. With one rnon-bonding pair, the shape becamnes see-saw. 4, (b) Baf, is a AX, type salt. In its crystal, Ba” ions are arranged in cep arrangement. Since there are two tetrahedral sites for each Ba"*ion and F ions occupy all the tetrahedral sites, there will be two F™ ions for each Ba” jon. Thus, each F~ is surrounded by four Ba", ie, the coordination number of F™ is 4. 5. (d) SiO} and PO both have tetrahedral structure. In SiO$, no.of electrons =14 + (6 x 4) + 4=50 InPOX, no. of electrons =15 + (8 x 4) +3=50 Because of the presence of same number of electrons, SiO%* and PO}, are isoelectronic. 6. (a) Total number of valence electrons in HF =149=10 The electronic configuration is 6,6 1s4,0.25?, G 25%, 2px! = x2py! 7. (d) The point group of NSF, is Cy. 8. (d) IM?" ion has a higher CFSE in an octahedral field compared to M* jon, normal spinel will result. M2" ion have a higher CFSE in a octahedral field compared to M* ion, inverse spinel will result. The general formula of spinel is A*B3O}. Among. the compounds Fe,O, (ie, Fe Fe,O,) and NiFe,0, have inverse spinel structure. 9. (2 In NaCl, per cent of defect depends upon the concentration of solution and its rate of evaporation. 10. (P) CaTiO, has perovskite type structure. Init, Tihas a coordination number 6. 11. (a) V* = [Aq 3d? se [11 Senxt 2 where, n= number of unpaired electrons 1 Sm2x Multiplicity = 25 +1= (2x) +1 L=%m,=424 when L = 3, orbitals F. Thus, the ground state term symbol for V** ion is °F. 12, (a) The symmetry elements that are present in BF, are G,6,,64, 3C). 13, (C) In XeOpF, there are 4 bond pairs and 1 lone pair. Its shape should be trigonal bipyramidal but there is a lone pair, and bond pair-bond pair repulsion is lesser than lone pairlone pair repulsion, so to attain maximum stability and to reduce repulsion, it has see-saw shape. F de | t Xe0,F,9-0-0— B ©8000 0886.9 AA O28. @ eoeeeccocc oer ncooeoo Chemical Bonding and Molecular Structures 14. (0) Sulphur in SF, is in + 4oxidation state. Out of total of six valence electrons of sulphur, two form a lone pait, The structure of SF, should be trigonal bipyramidal but due to the presence of oe fone pair it hhas see-saw shape (according to VSEPR theory). 15. (b) The bond angle of C1,0 is 110.10° and that of water is 104.45°. oe ee oe” LSS SreareatO,0 Sheet 0 16. (0) Nz (7+ 7=149 = 0?, 6 67, 028", 6 25°, n2py PF, 020; |= 13) = 0182, 15%, 62s”, 6 2s?, n2p? NE 7#7- » WOpp, 02p; Nitrogen has no unpaired electron, so itis diamagnetic while NJ has one unpaired electon, soit is paramagnetic in nature. 17, (@) Electronic configuration of Cis 6,6 b,a25?,6 2s, ndp? ~ np? Ny-N, 8-4 Bond order = +2 2 Since, all the electrons are paired, itis diamagnetic, 18, (b} CIF, has two lone pairs of electrons on the central atom, 19. (d) XeF, => 4bp + 2ip = 6 hybrid orbitals. Thus, the geometry of Xe is square planar because of the presence of two Jone pairs of electrons. e en ko aK 20. (d) Icosahedral structure is shown by boran compounds. Chemistry | 17 21. (@ Bromine utilized three out of the five sp’d hybridized orbital in Bf, 22, (b) InBF, the symmetry point group is Dy, 23. (b) NOCI has the following structure because of the presence of two bond pairs and one fone pair of electrons. N oF &, nzo | ie, ithas some dipole moment and is not chiral: NOC belongs tothe point group C, 24. (b) Bond order is reciprocal to bond length. So, the molecule with higher bond order will have shorter bond length. Bond order of Cy = 1 Bond order of Ny = IM, - Bond onder of 0, Bond order off, = 1 Ji, = Nel= 3INe-Nal N; has highest value of bond order, so it will have shorter bond length. 25. (@) In{SFC1,}*, $ és the central atom. (SFCL,I" =3bp + 1p =4 = sp? hybridization and thus, [SFCI,]* has trigonal pyramidal geometry. & a TN {5,0,]?" has the following structure in tthe lone pair does not repel the SO} group as S—S bond length is very large. Thus, its structure is trigonal planar. 26, (a) Shape of KeOF,]” is as xx aN Pentagonal monopyramidal18 | Chapterwise GATE Solved Papers A represents the central metal, i.e., Xe the X represents the number of sigma bonds between the central atoms and outside atoms, ie, between Xe and F or Xe and O. ‘The E represents the number of lone pair of electrons surrounding the central atom. 27. (4) The point group of CIF, motecule is Cay. Thus, the corresponding numberof irreducible representations is 3. 28. (d} 1M" jon has a higher CFSE in an octahedral field compared to M* ion, normal spinel will result. If M2* ion has a higher CFSE in an octahedral field compared to M* ion, inverse spinel will result. Fe,O, is composed of Fell) (ous) and Fell) (c) ions with d° and d> configuration, respectively. Since, d> has no CFSE, hence the structure is inverse. CoO, has asimilar structure with d” and d® configurations for +2 and +3 states respectively. Co”, i.,d° ion is low spin because ofits (a) high charge (even with weak ligands like oxo) and (b) maximum gain in CFSE. So, the structure is normal. 29, (a) In XeF, and [Sif,]* both, the hybridization of central atom is spd? as the former contains 4 bond pairs and 2 lone pairs while latter has 6 bond pairsi.e., {otal six hybrid orbitals. 30. (@) Since, the compound have 2-fold rotational axis and an inversion centre, two distinct symmetry ‘operations can be performed. 31. (0 The number of irreducible representations of the point group of the molecule is three (C>, $z, dy 32. (b) The point group of the resultant molecule will be Coy 33. (6) Density ofa unit cell, d = 2 *M a XN, 3.6: 2x 137.3 a x 6,023 x10 2x 137.3 3.62 x 6.023 x10 = 12.59 x 107? 30 x 10-7 10% Diagonal of any face = av2 3x10" 2 =23x10°8 x1.414 3x10 x1.414 .6 x10" Qn= Chemical Bonding and Molecular Structures & 34, (b) Due to the presence of six fluoride ligands and one lone pair of electrons in Xef,, the structure lacks perfect ‘octahedral symmetry and is disordered. In{XeO,]* all the valence shell electrons of xenon are involved inthe bonding with oxygen and hence, no lone pair of electrons is. present, So, it has perfect octahedral geometry. 35, (b) In zinc blende structure cubic closed packing is found. While in wurtzite structure hexagonal closed ge packing is found. & 36. (a) In Pb;O,, the chains of PbO, octahedra aligned v along (001) plane. The space between{PbO,] chains is occupied by loose pairs of Pb* ions forming tetrahedron. Thus, the crystal structure of Pb;O, contains both octahedral and tetrahedral units. 37, (b) Dipole moment = Charge x Bond distance @ 1.08 = Charge x 1,27 Charge = 1.08/1.27= 0.85 & Since, HCI is electrically neutral, H* and CI" will carry - the same charge with opposite sign, € 38. (C) In solid sodium chloride conduction band is not . empty. € a 39. (b) The structure of N(CH), is pyramidal and structure » of N(SiH,), is trigonal planar. This is because Si contains empty orbitals and utilised them in back bonding with N. 9 Sits N AN 407 | “oH, ‘sk = Hy ‘Sits 2 Structure of N(CH) Structure of NSH pyramica ‘gon! planar 40. (©) In d5s' configuration, there are 6 electrons. unpaired $0, Senxt=6x4 2°72 Multiplicity = 25 +1=@ x3) +1=7 & 3 4111 At 1 = Em, =+2+140-1-2+0=0 when L=0, orbital is $. So, the ground state term symbol is ”, Similarly, for d°, and multiplicity a e x 3 + = 6. Thus, the term symbol is 5@ 0 -0— 900C 0 6 e 6 G e 6S 6 @eeeaeococ eo Chemical Bonding and Molecular Structures 41. (@) Both CoFe,O, and FeFe,! structure, have inverse spinel 42. (a) MnO, has normal spinel structure, so the dipositive Mn®* occupy tetrahadral_ holes while tripositive Mn®* occupy octahedral holes. Thus, two Mn** ions are present in octahedral and oneMn?* ion found at tetrahedral site. 43. (a) IniBrz, number of hybrid orbitals, H = "[V+m+A-C] Iwhere; V= no. of valence electrons, M= no. of monovalent atoms, A and C = negative and positive charge respectively] Ha 742 41-9) fo=5 So, its hybridization is sp*d, and thus structure should be trigonal bipyramidal. But because of the presence of three lone paits of electrons its actual geometry is linear. § Go Linear geometry er Be InBrO;,H = 3740 4+ 1-0] = 4=ssp? hybridization. Thus, the structure should be tetrahedral. Q oe But its actual geometry is pyramidal due to the presence of alone pair of electrons. 44. (@) Oy has bent and Ny has linear structure. Chemistry | 19 45, (9 Ind ACD, AC? =a? +2? oMtAC = a 1 Ae? = ac? fect = (2a)? +a? = 3a? AE= 3a = a= Ba B rea 4 46. (a) Bond order of Ny =100-4=3 Bond order of O, = 20 ~ 6) =2 Bond order of Nz =J00-9=2 5 Bond order of 03 = a0 =N=15 Thus, the order is Nz >Nz> 0, > 0} 47. (b) Sibecause of the presence of empty d-orbital forms back bonds with lone pair of nitrogen. Thus, the lone pair is no longer available for donation or protonation, ‘While such a condition is not found in (CHs),N. So, (CH,) Nis more basic than (SiH) ,N and (SiH,),N has trigonal planar structure, pits as — ‘Trigonal planar structure of (Si),s-Block and p-Block Elements Syllabus s-Block and p-Block Elements Main group elements : General characteristics, allotropes, structure and reactions of simple and industrially important compounds : boranes, carboranes, silicones, silicates, boron nitride, borazines and phosphazenes. Hydrides, oxides and oxoacids of pnicogens (N, P), chalcogens (S, Se and Te) and halogens, xenon compounds, pseudo halogens and interhalogen compounds. Shapes of molecules and hard-soft acid base Concept. Structure and bonding (VBT) of 8, Al, SiN, P, S, Cl compounds. Allotropes of carbon : graphite, diamond, Cay. Synthesis and reactivity of inorganic polymers of Si and P. e ec GATE 2011 (1 Mark Questions) y Solution Points 1. Among the following, the group of molecules that undergoes rapid hydrolysis is @) Sf, AlCl, SiMe, (b) BCI,, SF, SiCl, (0) BCL, SiCl,, PCI, (4) Sk, AlCl, SiCly 2, The reaction of solid XeF, with Asf, in 1:1 rato affords (a) XeF, and As, (b) Xef, and AsF, (0) XeF]* (Ask) (6) [Xe] TAshg)” & GATE 2010 3. The Lewis acidity of BF, is less than BC, even though fluorine is more electronegative than chlorine. Itis due to (a) stronger 2p (8) ~ 2p (F) o-bonding (b) stronger 2p @) - 2p (F) r-bonding (c) stronger 2p (B) ~ 3p (Cl) o-bonding (d) stronger 2p (8) - 3p (Cl) xbonding 4. Pyroxenes are class of silicate minerals, which exhibit a polymeric chain structure, as shown below@ ©-0—- 000890900099 0000008089 @eooooc°e s-Block and p-Block Elements Its simplest repeating unitis a) (Si0,)*> (b) [SiO]? (0) [Si,0,1°° {8 151,0,)°" 5. The number of ‘framework electron pairs’ present in the borane cluster [B,2Hial™ is f@) 10 ) 11 (9 12 (d) 13 GATE 2008 6. White phosphorus, P, belongs to the (a) oso system (b) nido system (©) arachno system (@) hypho system GATE 2007 7. The Lewis acid character of BF,, BCI, and BBr, follows the order ‘@) BF, < BBr, < BCI, (b) BCI, < BBr BCI, > BBr, (b) BB, > BCI, > BF, (© BF; > BBr, > BCI, (@) BBr, > BF, > BCI, 16, Among the following diatomic molecules, the one shows EPR signal, i, @ li, () By oc, @N; GATE 2011 (2 Marks Questions) ‘Common Data for Questions 26 and 27 NajHPO, and NaH,PO, on heating at high temperature produce a chain sodium pentaphosphate quantitatively. 17, The ideal molar ratio of Na,HPO,, to NaH,PO, is @ 4st (b) 1:4 © 3:2 (d) 2:3 18, The total charge on pentaphosphate anion is @-5 03 @-7 @ 9 GATE 2010 19. The most populated rotational state for HCl (B = 8.5 cm”) at 360 Kis @2 b) 3 5 @7 GATE 2007 20, The reaction of ammonium chloride with BCh, at 140°C followed NaBH, ives product X. The formula of Xis (@) BN,H, (b) BNsH, (0 BNGH,, (@) BH...NH], 21. Which ofthe following statements islare true for X° (i)Xis not isoelectronic with benzene. Gi) X undergoes addition reaction with HCL (ii) Electrophitic substitution reaction on X is much faster than that of benzene. (iv) X undergoes polymerization at 90°C. (@) (and (ii (b) (i only (0) Gi and (i) (@ @and (iw) ‘s-Block and p-Block Elements v Solution Points @s-Block and p-Block Elements \ 22, The correct classification of [B;Hs]-, Bet and BsH, respectively is {@) closo, arachno, nido (6), arachino, closo, nido (©) closo, nido, arachno—°, ;- (@) nido, arachno, closo Statement for Linked Answer Questions 23 and 24 Triphosphazene is prepared by reacting X and Y in equimolar ratio at 120-150°C using appropriate solvents. @ © O_ Q \ 23. The reactants X and Y respectively, are eS 6 (@) PCh; NH, ; tb) PCL; NHS 6 (© POs: NHAC uy (d) PCI; NH,CI © , , 24, The structure of triphosphazene is © qa i Se @ wy © oN a , al fea PP. © AYE av Ww H,80, + 3HCI | SiCl, + 4H,0 —> H,SiO, + 4HCI e PCI, + H,0 — POCI, + 2HCI 0 e paar? HyPO, + HCI ‘ [Note AI,C\is soluble in non-polar solvents} 2. (€) XeF, (Keron difluoride) acts as a fluoride donor and thus, forms complex when mixed with covalent pentafuorides fike AsF, XeF, + Asfy —> [XeF]* [ASF] ve 3. (b) In Bry, boron has a vacant 2p-orbital and each | fluorine has completely filled unutilsed 2p orbital Fluorine transfers these two 2p-electrons to vacant 2p-orbital of boron. This bond reduces electron deficiency of boron and hence, also the Lewis acidity Tendency of formation of such bond is more in fluorine due its small size. 4, (b) Inpyroxeres, there is @ total of 3 oxygen atoms per silicon atom, so the simplest repeating unit is [SiO,}*" or (Si0,)™. 5. (d) In[B,3H,.] anion, m = 12 (where m = number of BH unit. According to Wades’ rules, each BH unit contributes two electrons tothe framework bonding in the borane and the negative charge is also assumed to be used up inthe framework bonding Thus, the total number of electrons in © e © Cc Butyl” =12x24 2 =2442=26 ea neestive He, Se “Thus, the number of electron pairs = 2 =13 6. ib) P, molecule has tetrahedral structure. According to Wade, one Ps equivalent to BH, So, Py =(BH,), = B,Hy or BH} “Thus, it should belong to nido system. 7. (0 In boron tihalide, BF, is least acidic. Due to its small size, Fhasa tendency to back donate is lone pair @0©e0000°00 Answers with Explanations of electrons to B. Due to this electron transfer, the electron deficiency of B is reduced. Such tendency to back donate the efectron pairs least in Br. So, the order of acidity is BBr, > BCl, > BR, = (b) The primary unit of BaTilSi,O,) or (SiO§) is 10. MW. 2, 1B. 14, (SiO,)*" (asn = 3). Thus, it is formed by sharing of wo ‘oxygen per Si atom and results in the formation of cyclic silicate (a) Chrysotile (Mg, SisQro(OH)q) is commercially known as asbestos, (@) Triple superphosphate is produced by the action of 54% phosphoric acid over phosphate mineral Cay(PO4), + 4H5PO, —+ 3Ca(H,PO,) (b) Phosphorus acid (HPO) has two OH groups. ° [som Hor 7 eon vd (@) BH,-COis more stable then BF, CO because BH, is a soft acid and CO is a soft base and soft acids react faster and form stronger bonds with soft bases (6) Borazine can be prepared by using NH,Cl BCI, and NaBH,. It is a two-step process. In the first step , NH,Cl and boron trichloride react together to give ttichloro borazine in chlorobenzene solvent. 38Cl, +3NH,Cl— CyB,HyN, +9HCl In second step, B—CI bonds are subsequently converted to BH bonds. 2C1BjH,Ny + 6NaBH, —> 28,H,N; + 3B,H, + 6NaCl (€) Though ionization potential increases on moving ‘across the period as nuclear attraction increases but phosphorus has haltfilled 3p orbital and Mg completely filled 3s orbital which are more stable than incompletely filed orbital. Thus, a large amount of energy is required to remove an electton, Thus, !£ of S is less than that of P and IP of Ali les than that of Mg. Order of IEis A BCl> BF, 16. (b) EPR signal is given by paramagnetic. species. Liz, C, and N, have no unpaired electrons and are diamagnetic. B contains unpaired electron and is, paramagnetic, soit can give EPR signals. 17. (d) When Na,HPO, and NaH,PO, are heated in the ratio of2 :3,a chain sodium pentaphosphate is formed. 2Na,HPO, +3NaH,PO, —>Na,P.Oy, + 4H,O sodium pestaphosphate 18. (6) Sodium pentaphosphate is Na,PsOys- Thus, Pentaphosphate anion is PsO%,,,i.e., this anion carries ~T charge. 19. (b) Most populated rotational state, 6.6 x10™ x 3x 10° x 6.5 x 100) =1.68 x10? | 2x1.38 x10 «300 _ | 2) 1.68 x10 Fn 1 1 =s[7-=-x6=3 yeaa 20. (b) Preparation of borazine isa two-step process. n this Process, boron trichloride is first converted to trichloroborazine. 38Cl, +3NH,Cl— C1B,H,N, + 9HCI The B—Cl bonds are subsequently converted to B—H bonds. 2C1,ByH.Ny + 6NaBH, —> 2BsHsN, +3BH, + 6NaCl 21. (b) X is borazine. it is isoelectronic with benzene. It Feacts with hydrogen chloride to give an addition product. ByNjH, +3HCI—> ByNjHy Ch, 22. (©) The formulae for closo, nido and arachno borane are ([B,H,]”",B,H,, « andB,H,,¢ respectively. Thus, [BsHs]* is a closo borane. BH, [BsHs, 4] is a nido borane and B,H,, [BHs, ¢] is a arachno borane. s-Block and p-Block Elements 23. (c) Triphosphazene is prepared by reacting PCIs; NH,Cl in equimolar ratio at 120-150°C. A halo hydrocarbon is used as solvent. PCI, +nNH,Cl—20-182°C *, (NPCI,],, + 40 HCL 24, () Structure of triphosphazene is as ad oa NZ K \ Rf “y avll rel ca \7 “el 25 (b) The overall charge present on Si,Qyg is ~12 as x=6 in (SIO,)?°. 26, (d) By the reaction of PCl, and NH,C| substances with the empirical formula PNCl, are formed, which ‘on purification by sublimation gives mainly the trimers (PNCI,), and tetramer NCI) - nPCl; + nNH,Cl 32°C (PCI, + 4nHHCl 27. (c) According to Wade's rule, carboranes are obtained H unit by CH* unit. So (0 [BtiCor [Butte 85 Bolo, eae Ai [CHF or [ByH, BAY or HCH [Bi 28. (d) When Xef, is hydrolyzed in a strongly alkaline medium a major portion is precipitated as perxenate salt (XeO}"), 29, (a) Talc is Mg,Si,Qj9(OH)2 and its hardness is less. Moscovite is KAI,AISi,Oj9(OH)2, its hardness is intermediate. Margarite is CaAl,AISi,O,o(OH), its hardness is high. 30, (b) Structure of Bi gCjHi2 is icosahedral (closo structure}. It exists in three isomeric forms. They are orthocarborane (1, 2-C)ByoH,2), metacarborane (1, 7- C,ByoHy), paracarborane (1, 12-C,ByoHy9). & 31. (b) According to Wade's rule, boranes having a formula of (BH)? show closo structure. So, out of the given compounds, B,.H?5 will show closo structure, 32, (d) In archno structure, the formula ByHyyg is used. gs Alternative [BH] satisfies this condition.Transition Elements Syllabus ‘Transition Elements General characteristics of d and f-block elements ; Coordination chemistyy : structure and isomerism, stability, theories of metal-ligand bonding (CFT and LFT), mechanisms of substitution and electron transfer reactions of coordination complexes. Electronic spectra and magnetic properties of transition metal complexes, lanthanides and actinides. Metal carbonyi, metal-metal bonds and metal atom clusters, metalocenes ; Transition metal complexes with bonds to hydrogen, allyl, alkenes and arenes ; Metal carbenes ; Use of organometaic compounds as catalysis in organic synthesis. Bio inorganic chemistry of Na, K, Mg, Ca, Fe, Co, Zn, Cu and Mo GATE 2011 (1 Mark Questions) 1, John-Teller distortion of CuSO,-5H,Oacts 10 (@) raise symmetry (6) remove an electronic degeneracy (0) cause loss of H,0 ligand (4) promote a electron to an antibonding molecular orbital 2. A.well known naturally occurring organometallic compound is {@) vitamin B,, coenzyme {b) chlorophyll (@) cytochrome P-450 (d) myoglobin 3, The complex that exists as a pair of enantiomers is (a) trans- [CotHNCH,CH,NH,), Cl] (b) cis{Co (NHs)4Clal” (©) [PUPPhy) (Cl) (Br) (CHy)} (@) (ColH,NCH,CH.NH,),]" 4, The red colour of oxyhaemoglobin is mainly due to the (@ d-d transition (6) metal to ligand charge transfer transition (6 ligand to metal charge transfer transition (d) intraligand rt transition ¥ Solution Points28 | Chapterwise GATE Solved Papers GATE 2010 5. Structraffy nickelocene is similar to ferrocene, Nickelocene attains stability due to the formation of {a) a mono cation (b) adi cation (3) ammono anion (@) adi anion 6. Among the following pair of metal ions present in nature, the first one functions as an electron transfer agent and the second one catalyzes the hydrolysis reactions. The correct pait is (@) Feand Zn (b) MgandFe (0 Coand Mo (@) Caand Cu GATE 2009 7. The correct statement about the Cu—N bond distances in {Cu(NH3)6]”* is {a) all the bond distances are equal (b) the axial bonds are longer than the equatorial ones (©) the equatorial bonds are longer than the axial ones (d) all the bond distances are unequal 8. In the transformation af oxyhaemoglobin to deoxyhaemoglobin {a} Fe* in the low spin state changes to Fe?” in the high spin state (b) Fe in the low spin state changes to Fe”* in the low spin state (0) Fe’ in the high spin state changes to Fe** in the low spin state (d) Fe** in the high spin state changes to Fe”* in the high spin state GATE 2008 9. In biological systems, the metal ions involved in electron transport are (@} Na* and k* (b) Zn andMg* > (©) Ca®* and Mg (@) Cu and Fe 10. The structures ofthe complexes {Cu(NH,) ,(CIO,)2 and {CuNH,),1IC1O,) in the sotution respectively are (a) square planar and tetrahedral (b) octahedral and square pyramidal (€) octahedral and trigonal bipyramidal (@) tetrahedral and square planar 11, The spectroscopic ground state symbol and the total number of electronic transitions of [Ti(H,O}e]** are (a) Typ and 2 (b) *Agg and 3 (0 3Ty and 3 (d) FAzg and 2 12. Metal-metal quadruple bonds are wellknown for the metal @ Ni (6) Co (9 Fe (d) Re 13. The magnetic moment of [Ru(H,O},]** corresponds to the presence of {a) four unpaired electrons (b) three unpaired electrons (0. two unpaired electrons (€) zero unpaired electrons Transition Elements b , y Solution Points ©) aTransition Elements GATE 2007 14. In photosynthesis, the predominant metal present in the reaction centre of photosystem # is (a) Zn &) Cw (9 Ma @ Fe 15. The octahedral complex/complex ion which shows both facial and meridional isomers is (a) trighycinato cobalt (I) (b) tris (ethylene diamine)) cobalt (tl) (© dichloro diglycinato cobalt (Wl) (@) trioxalate cobaltate (1) e « 6 @ a © 6 e e 16. The difference in the measured and calculated magnetic moment (based on spin-orbit coupling) is observed for (a) Pm?* (b) Eu* (o Dy* (@ Lu* “GATE 2006 17, Iron-sulphur clusters in biologicat systems are involved in (2) proton sransfer (b) atom transfer (2) group transfer (@) electron transfer 18. The correct statement regarding the thermodynamic stability and kinetic reactivity of metal ion complexes is that (a) more stable complexes are less reactive (b) there exists a dependence on the bulkiness of the ligand (C) there exists no direct relation between these two phenomenon (d) there exists a dependence on the size of the metal ion GATE 2005 19. The complexes [Co(NH,)_(H,O)CIBr, and [Co(NH,),BmICI-H,0 are examples of (a) ionization isomerism (b) linkage isomerism (c) geometrical isomerism (d) optical isomerism 20, In the trigonal bipyramidal crystal field, the d orbital with the highest energy is @ dy dd Ody a? oS e e€ © e 6 © © 21, The metal present atthe active site ofthe protein carboxypeptidase A is (@) zine (b) molybdenum eS (Q magnesium (d) cobalt e 22, The neutral complex which follows the 18-electron rue is (@) (nf - CyHs) Fe(CO), (0) (n° = C5Hs) Mo(CO), e (0 NP - CsH5)2 Co (d) 5 - CsHg)Reim® - CoH) Chemistry | 29 ¥ Solution Points30 | Chapterwise GATE Solved Papers GATE 2004 23, The absorption of [Co(NH,),]”* is (@) stronger than that of [Co(NH,)5 Cl?" (b) stronger than that of {MnCl,]°~ (weaker than that of MnC1,]?" but stronger than that of (Co(NH,) Cll” (d) weaker than those of both [MnCl,]? and [CotNH,} Cl" 24, The umber of metal-metal bonds present in Iry(CO},, are 4 5 @6oX es GATE 2003 - an 25, The ligand field bands of lanthanide complexes are generally sharper than those of transition metal complexes because {@) transitions are allowed for lanthanide complexes (b) intensity ofthe bands are higher for lanthanide complexes (6) Forbital have higher energy than d-orbital (d) Fotbital, compared to orbital interact less effectively with ligand 26, Nature has chosen Znill) ion at the active site of many hydrolytic enzymes because fa) Znill) is a poor Lewis acid {b) Zn(II) does not have chemically accessible redox states (© Znitformns both four and higher coordination complexes (@) Znild forms weak complexes with ox\ggn donor ligands f oy vaATE 2002 27. Electron transfer from Fe(Ht,0)2* to Fe(H,O)3* is likely to occur via (@) dd transitions (b) inner sphere electron transfer (€) Sytmechanism (¢) outer sphere electron transfer 28, The complex formed in the brown ring test for nitrates is (a) [Fe(Ht,0);NO}* (b) [Fe(H,0),NO]* (© FFett,014(NO))* (@) [FelH,0),(NO)* 29, The complex which obeys the 18-electron rule is {@) Fe(CO),, (b) Ni(CO),(PPh) (9 Crco), (@) CrCsHs)2 30. The existence of two different coloured complexes of Co(NH,) Cl, isdue to (2) optical isomerism (b) linkage isomerism (2 geomettical isomerism (d) coordination isomerism = GATE 2001 31. The chromium (Il) species formed soon after electron transfer between IrCl and CKH,O1E is @) CoH, (b) Crt, 0)5CP* fa cree (@) Cr(H,0), Cl, Transition Elements vy Solution Points AA AR e é S800090 ae CS e e e S 6 Transition Elements 32. The metal ion present in carbonic anhydrase is (@ Me (b) Zn 0 Gu @) Fe GATE 2000 33, The compound which exhibits John-Teller distortion is (2) [Min(H1,0),)** (b) Ma(H,0),)* (0 [CHH,0),)* @ [FelONgI 34, The compound which obeys 18-electron rule is (@Mn(CO, (0) FCO}, , (© VIC), () CHCO), GATE 2011 (2 Marks Questions) 35. The crystal field stabilization energy (CFSE value for TitH,O* that has an absorption maximum at 492 nm is (a) 20325 em (b) 12195 em (c) 10162 cm" (¢) 8130 cm 36. In the isoelectronic series, VOY, CrO} and MnO;, all members have intense charge transfer (CT) transitions. The incorrect statement is (@) CT transitions are attributed to excitations of electrons from ligand (6) to metal (2) (b) MnO; exhibits charge transfer at shortest wavelength among the three (©) The wavelengths of transitions increase in the order VOF < CO} (b) (CH,CO)Mn(CO) ,{"°CQ) (0 (3CH,;CO)Mn(CO), (d) CHsMn(CO) , GATE 2010 40. The number of unpaired electron (s) present in the species[Fe(H,0) ,(NO}]* whici is formed during brown ring testis @2 ) 3 10 4 @s Chemistry | 31 v Solution Points32 | Chapterwise GATE Solved Papers 41, The dd absorption band of [Fe(H;0),]* is split due to (a) presence of octahedral geometry (b) static John-Teller distortion (0 dynamic John-Teller distortion (@) presence of trigonal bipyramidal geometry 42, The crystal-field symbol for the ground state of (Mn(CN),]*> is @ "hg ) Ag ( %e, (@ SA 43. [CoCl,]*" is a blue coloured complex. Controlled-treatment of this complex with water generates two isomeric light pink coloured complexes of composition {Co(H,O), Cl,]. Identify the correct point groups for {CoCl.,]?> and two isomeric complexes {CoVH,0) Cl} (@) Day and (Coy and Cy) (b) Ty and (Cy, and Dy) (0 Dyy 2nd (Coy and Dy) (d) Tyand (Cy, and C,y) ‘Common Data for Questions 44 and 45 A six-coordinate transition metal complex is ESR and Mossbauer active, The effective magnetic moment of this complex is ~ 5.9 B.M. 44, The metal-ion along with its oxidation state and the number of unpaired electrons present are @) Fett and 4 (b) Mai) and 5 (©) Feilll) and 1 (@) Fe(llt) and 5 45. The complex is (2) [Mn(H,0)_)** (b) [Fe(CN)gI (© (Fe(H,0),)" (@) [Fe(H,0),]" Gate 2009 ‘Common Data for Questions 46 and 47 Treatment of W(CO}, with l equivalent of Na(CjH,) in THF solution gives the ionic compound M, Reaction of M with glacial acetic acid results in product N. The 'H NMR spectrum of N displays two singlets of relative intensity 5 : 1 ‘When Vis heated, hydrogen gas is evolved and Q is produced. O may also be prepared by refluxing WiCO}, with cyclopentadiene and H is also produced. Treatment of O with an equivalent of Br, produces P. (Use the 18 electron rule as your guide) 46, The compounds M and N, respectively are (@) {(CsHs)W (CO),)Na and [(C;Hs)W(CO) HI (b) {(CsHs)W(CO) ,JNa and [(CsHs)W(CO) , H] (6) {{CsHs)W(CO),]Na and [(C,H)W(CO} gH] (4) (CH) W(CO) Na and [(C,H,)WICO),H} 47. The compounds O and P, respectively are (@) {(C,H,)WiCO}s}y and [(CsHs]W(CO),8r] (6) {{C,H,)W(CO} J and [[C,H)W(CO) ,Br THF) (6) [(CH)W(CO) (THF)] and [(C,H,)W(CO), Be] (€) UCSHs)W(CO)3], and (C,Hs) W (CO) Br(THF)] Transition Elements y Solution Points € @ @6 © e 6 & e © © 6 Transition Elements GATE 2008 Statement for Linked Answer Questions 48 and 49 In the reaction, (PPh)sRhCl HS. x+y 48. Compound Xis PPh; PPh; (@) PhyP—Rh—Cl to) PhyP—Rh—PPhs N==CCH, a ic) onypti—teh, @ rhe —PPhy H,C—= CH 49, RhiPh3)3Cl reacts very fast with 2 gaseous mixture of Hy and CH, to immediately give Z. The stucueof Zi, Phy (a) H;C—CH, Rh PhP™ PPh; I (©) (Phy) 2RhCI(n? - CzH,) (d) PhyP—Rh—PPh;, | GATE 2007 50. The separation of trivalent lanthanide ions, Lu", Yb*, Dy**, Eu can be effectively done by a cation exchange resin using ammonium o-hydroxy isc-butyrate as the eluent. The order in which the ions will be separated is (a) Lu*, Yb, Dy, Eu (b) Ev", Dy”, Yb*, Lu (c) Dy*, Yo, Eu, Li (@ Yb™, Dy** Lu, Eu* 51. Arrange the following metal complexes in order oftheir increasing hydration energy [Mn(H,0),]* — [V(H,0)_]"* ——INi(H,O)g]* ——_FTIH,O}6]”* P Q R 5 @P [Co(NH,)<(H,O)]" + [CrCIH,0)5]* 2.[Fe(CN)g]*~ + [Mo(CN}g]** —> [Fe(CN),)>> + (Mo(CN),]*- Which one of the following is the correct statement? {a) Both involve an inner sphere mechanism (b) Both involve an outer sphere mechanism Chemistry | 33 y Solution Points«34 | Chapterwise GATE Solved Papers Transition Elements (©) Reaction 1 follows inner sphere and reaction 2 follows outer sphere | ¥ Solution Points mechanism - (@) Reaction 1 follows outer sphere and reaction 2 follows inner sphere mechanism 53. The compound which shows L ” (0 V,05 (d) TiC, in the presence of AIC3Hs)s 57. In the reaction shown below, X and Y respectively are Mng(CO)j) “> (x) —SESSEEE9(¥) (a) [Ma(CO) ]?”, [CH,C(O)Mn(CO)} 5)~ (b) [Mn(CO),1", ICHClO)Ma(CO} 5] @ (© IMn(CO),}”, [CKCO)s] (4) [Mn(CO) 4}, [CIMA(CO) 5] 58. W(CO), reacts with Mel. to give an intermediate which upon treatment with CHAN; gives a compound X, X is represented as (a) WMe, (b) (CO); W—Me (<) (CO); W=C(MelOMe (d) (CO); ‘CMe é GATE 2006 59, In biological systems, the metal ion involved in the doxygen transport besides Fe is Se (2) Co () Zn (0 Mg (@) Cu 6 60. The set of ions expected to show John-Teller distortion in their complexes is (@) Tid, Cuttn, High-spin Fett) {b) Cut), Ni(l), High-spin Fe(tl) (©) Cult), Low-spin Feil), Ti(t) (d) Low-spin Fett), Mat), Cut) 61. The comlexes [Co(NH,),(H,O)CIBr, and [Co(NH,)Br,} CI-Hz0 are examples of {@) ionization isomerism (6) linkage isomerism (0) geometrical isomerism (@) optical isomerismS9SPOCooOoooeoeeosds e © © eS .| ©) e © © e © e Transition Elements GATE 2005 62, {Co(CO)4]is isolobal with (@ CH, a, (9 CH, (a) CH 63. Ligand field stabilization energies are smaller for lanthanides compared to transition metals in the same oxidation state because {@) size of lanthanide ions are larger (b) Forbitals interact less effectively with ligands (c) size of lanthanide ions are smaller (d) lanthanides favour oxyger.donerfigands. 64, The lanthanide complex...ovhere,..acac = acetylacetonate; phen | 10-phenanthroline) that do not have square antiprismatic structure is (@) {Ce(NO,),] (b) [Lalacac),(H30) ] (0) (Celacac),] (@) (Euacac)s(phen!] 65. The values of M—C stretching frequencies of (}[V(CO),} (ill [Cr(CO},] and (ii) {Mn(CO),]* follow the trend @ Gi) > > Gd © (i) > Gid > @ (© @> > Gi) @ Gin > > O 66. For the complex ion [Cu(NH,},]”*, the coordination geometry will be (a) octahedral (b) tetragonally distorted octahedral (© trigonal prismatic (@ trigonal antiprismatic 67. In.Q 66. the number of possible d-d transitions will be {@) one () two (© three @) four GATE 2004 68, The most suitable route to prepare the trans isomer of [PICl,(NH,)(PPhy is (a) [PtCl,]*" with PPh; followed by the reaction with NH, (b) [PtCI,]* with NH; followed by the reaction with PPh, () [PUNH,),]°* with HCl followed by the reaction with PPh; (d) [PtNH,),]°* with PPh, followed by the reaction with HCI 69. The number of absorption bands observed in [Fef,]" and (Cof,]*”, respectively are (@) t and 3 (b) Oand 1 (© Oand3 (@) 3and1 GATE 2003 70, [COCI(NH,)5]”* + [Crit#;O),]”* [Cott,O}NHy}5]* + [CrCH,0) 51" The correct statement regarding the above reaction is that {@) itfollows outer sphere mechanism (b) itfollows inner sphere mechanism with NH acting as the bridging ligand (c) itfollows inner sphere mechanism with CI acting as the bridging ligand {d) it snot an electron transfer reaction Chemistry | 35 y Solution Points36 | Chapterwise GATE Solved Papers GATE 2002 71. The complexes ViCgHg)2 and Cr(CcH,), are both readily oxidized in air to their respective cations. The number of unpaired electrons, respectively in each are 0,0 1,0 ot @1t 72, The metals involved in nitrogenase are (@) Fe and Mg (b) Moand K {) Moand Fe (d) FeandK GATE 2001 73. Amongst the following, the strongest oxidizing anion is fa) COP (6) voy (9 FeO} (d) MnO} 74. The compound which has four metal-metal bonds is (2) Fe,(COly (b) Co,(CO), (0 [Re,Cl,]* (d) Ru;(CO), GATE 2000 75. The complex with spin-only magnetic moment of ~ 4.9 BM is (a) [Fe(H,0)_]* (0) [Fe(CN),}*~ (b) [Fe(CN) (0) fFe(H, OP Transition Elements y Solution Points@| | e © Se 200 @©ee @enoeoeoode @eoee co Answers with Explanations 1. tb) in CVSQ,, “5H,O, Cuis present as Cu". cu” =a 3? a de ATT (Octahedral spliting Degenerate cottitals 4. (a) When oxygen is bound to Fe* in heme, ali the electrons of the Fe atom are forced into the three lower energy fa, orbitals and it produces low spin ‘oxyhaemoglobin. In oxyhaemoglobin, Fe™* = [Ar] 34° Ol [ETAT % (en EI By pe Bane ‘oin-Toler distortion be or TATA] It is clear that the two out of three electrons in ey orbitals can occupy eitherd,. orbital ord _,2 orbital. Since, thee, levels not symmetrically filed, lohn-Teller distortion occurs This removes the degenetacy of the e, andi, levels. Thus, the complex is distorted. 2, (a) Vitamin B,, coenzyme is a well known naturally ‘occurring organometallic compound. 3. (d) Complexes of the type [M(aa),], [Mlaa), b.], Miaa b,c,) exkibit optical isomerism and exist.as a pair of enantiomers Thus, [Co(H,NCH, CH;NH,)3]* exists as a pair of enantiomers. The structure of its enantiomers are as | Enartiomess of fOofen) | UAT ‘The sharp high enerBy transition between tz, and e, levels ofthe d-lectrons is responsible forthe bight red colour of oxyhaemoslobin, 5. (b) Nickelocene attains stability ue tothe formation ofa Gi cation a8 it contains twa electrons in its antibonding molecular orbital, which ae easy to remove. 6. (a) Feactas electron transfer agent in many processes. Zinc (as carboxypeptidase) act as catalyst in hydrolysis reaction specially in enzymatic reactions, 7.(b) In (CuNH,}g]"", the geometry is distorted ‘odahedral due to JobTeler distortion and axial bonds distances are larger than equatorial bond distances. 8. (@) In deoxyhaeroglobin, the Fe™ is in the high spin state and is paramagnetic. When an oxygen molecule binds fo the iron atom of a heme group through its vacant sixth coordination site, the Fe atom becomes Tow spin, Thus, the transformation of oxyhaemoglobin to deoxyhaelmogicbin involves the change in spin state of Fe”* from low to high. 9, (d) Cu® and Fe®* metal ions are involved in electron transport in biological systems 10. (2) [CuINH)4] (CIOd2 oF (CuINH)I* contains 4s fp a [cuNHy),* = {49 1 fs 4 moe) C4) CEL wy A= ur per38 | Chapterwise GATE Solved Papers (NH, being strong field ligand transfer the upaired alectton to 4d orbital.) In [CuNH,),] ClO, or [CuINH,},]*, Cu is present as. Cut ion. Cut = {Arg 3d"? 45° 4p" [Cu(NH,)* = (Ad 31° ‘$9 = tetrahedral (completely filled orbitals are highly stable, so NH ligand occupy us and up orbitals.) 11. (a) The spectroscopic ground state symbol of [TitH,0),]** is "Tyg. In this compound, there will be two electronic tra Ag (F) from 62) 3 La, (P) rom ty €5) 9 ptr i ~3Tg (F) (tom tf) e ‘The third electronic transition *T,, (F) —9 *Az. refers to the simultaneous excitation of both the electrons fromt,, toe, orbitals and is forbidden, 12, (d) Quadruple metal-metal bond is found in Re because it is a member of 5d series, 13. (d) [Ru(H,O),]* is a low spin d® compound, it has ero unpaired electrons. 14. (c) The predominant metal present in the reaction centre of photosystem II in photosynthesis is Mn. 15. (c) Complexes of the type[ Maa xb] show geometrical or facmer isomerism. (where, aa = bidentate ligand and a and b are monodentate ligands) ‘Among the given, dichlorodiglycinato cobalt (I), i, [CoCl,(gly)_] is such salt, so it will show fac and mer isomerism. alee) ov 16, (b) ForEu* the observed value of magnetic moments 3.4 while calculated value is 3.6 17. (@) lron-sulphur clusters involved in electron transfer. Transition Elements 18. (c) Thermodynamic stability is a measure ofthe extent to which the complex will form. tt depends upon the metal-ligand bond energies, stability constants et. iinetic reactivity, on the other hand, refers tothe speed with which transformations leading to the attainment of equilibrium will occur. It depends upon the activation energy. Thus, these two, ie, thermodynamic stability and kinetic reactivity, have no direct relation. (A stable complex may be inert or labile or an inert complex may be stable or unstable.) (a) The given compounds (Co(NH),(H;0)CIBr, and [Co(NH,),Br,JC!-H,0 exhibit ionization isomerism because’ in ionization isomerism, compounds having same formula differ in their ionic arrangement in solution. The difference occur because of the difference in ions, that are found in the inner and outer coordination sphere of the complex. These complexes also show hydration isomerism, 19. 20. (d) In trigonal bipyramidal crystal field, the d_ orbital has the highest energy. * Energy “eigonal bipyramidal 24 (@) Zinc metal is present atthe active site of enzyme carboxypeptidase A. 22. (d) (nF — CyHs) Rett’ ~ Cg Hg) follow 18-electron rule as it contains 18 electrons. Number of electrons are calculated as (n° - CyHy)Fe (CO), =5 +8 +4=17 (n’ - CsHg)Mo(CO), =5 +6 4+6=17 In? = CsHs), Co= 1049 =19 (n> ~ CyHs)Re tn? - CH) =5 +7+6=18 23. (b) [Co(NH,),]* contains Co™* Co = [Ar] 3d” aq? [Co (NH)? = [ITE 11114) TO lA] 41414 ]}-—— Iso AAT @ @6 © Transition Elements 29 (CFSE = 0.46 +06 X1=-2.4+0.6=-18 In{Co(NH,); Cl]?", cobalt is present as Co™. Go* = [Ar] 3d° aa (CotnHy),ciP* = [AAA] 414 6 oe) © ATA }-— ls. e TELE) e CFSE=-0.4x6=-24 In [MnC1,]?”, Mn is present as Mn”*. ; Mn = [An] 3d5 e moc = FT G tun @ STEIRIEIEE I Ti CFSE=-0.6x2+04x3=0 24, (¢) Number of M—M bonds are calculated as =2xm+An+2L=Zn where, m= number of M—M bond A-=atomnic number of metal atom n= number of metals in the formula L =number of CO ligands Z =atomic number of nearest inert gas 2XX4 77x 44212 =86X4 2x +332 =344 xe? 2 Thus, it has 6 metal-metal bonds as eeeeaenreccgvoonagooeo Chemistry | 39 25. (4) Electron in f-subshell do not screen the nuclear charge effectively so the nuclear charge increases, With this increase, there is a decrease in size and thus, electronic repulsion increases. $0, chances of interaction with the ligands become less. 26. (@) Zinc can form complexes with oxygen donor complex, e.g., in carboxypeptidase it forms complex with CO, 27. (d) In outer sphere electron transfer no bond making! breaking or ligand exchange takes place. So, the following se exchange reaction [FetH,O)?* + FetH,O).1* — FeiH,Ol.)* + [Fe(H,0),]”* ill proceed via outer sphere electron transfer. 28. (b)_ The brown ring test is used to detect he presence of NO} radical. In this test we add freshly prepared ferrous sulphate solution to the salt solution and then conc. H,SO, is added through the walls of the tube. A brown ring is formed at the junction of the two solutions. The reactions, involved in the test are NO; +H,S0, —>HSO; +HNO, 6Fe** +3H,SO, +2HNO, —> 6Fe™ + 44,0 +2NO Fe* +NO + 5H,O —>[Fe(H,0),NO|* dk browa rng 29, (d) Compounds containing 18 electrons, follow 1Belectron rule, Number of electrons are calculated as @ Fe(CO), = valance electrons offe + 2 x no. of CO ligands =842x4=16 {Fe has 3d° 4s? outer configuration] (6) Ni(CO),(PPh,) =10 +2 x3 +2x1=18 (0) CCO), =6 +2x5=16 ) Cr(CHy), =6 +2 x5 =16 [one CsH, donates 5 electrons] 30, (€) Complex Co(NH;),Cly exhibits _ geometrical isomerism. Cis isomer is violet while tans isomer is green in colour. r a Nis NA ae | SNH i NHS L cis [(Co[NH3)4Ciz)} trans ((Co{NHs),Cle)] (nt (geen)40 | Chapterwise GATE Solved Papers 31, (a) The reaction between IrCl}” and CxH,0)2* takes. place via inner sphere electron transfer mechanism, ‘The products formed are {IrCl, > and Cr(H,O)2". The reaction is Incl” + CrtHt,0}3* — (Ch, }* + CrH,0)3" 32. (b) The metal ion present in carbonic anhydrase is zinc. 33. {b) Jahn-Teller distortion is exhibited when the d-electrons are asymmetrically arranged as they repel some ligands in the complex more than others. In (Mn(H,O0).)" dd =electrons are arranged asymmetrically as ds dsp [Mn (H,0)}9* = [Aq] Conn or ALAA te iy Ope dog Thus, it exhibits John-Teller distortion. 34, (d) Complex compound which contains 12 valence electrofs, obeys 18-electron rule. Mn(CO), = 7+2x3=13 Fe(CO), =8 +2x 4=16 VCO), = 5426517 CHCO}, =6 +2 x6=18 Thus, CCO), obeys 18-electron rule. 35. (a) Absorption maximum, 2. = 492 em = 492x107 cm 1 CFSE (in em “y92x107 = 20325 em”! 36, (b) CT (charge transfer) transitions are attributed to excitations of electron from ligand to metal or vice-versa. | Transition Elements Higher the oxidizing power of metal, higher is the wavelength of transition, Order of oxidizing power is ve Cr < Mal The order of wavelength of transition is, VO} < ClO} [(C;H,)W(CO),] Na {(CsH)W(CO},] Na + CHyCOOH —> [(CsH5)W(CO),H] In[(CsH)W(CO),] Na, no. of electrons =546+Q2xI 41218 Inf{C,H,)W(CO) H], no. of electrons =6+6+Qx9+=18 ‘Thus, both obey 18-electron rule. 47. (A) (CH) W(CO), H] —“# [(CgH,)W(CO);]2 (P+ WCOY, > UC HWICON, (CoH, WICO)g], + Br; > 2 1CH_)W(CO}, Be PPh, 7 | (b)(PPh,),RhC| S25 PH,P—kh—PPh, I Nes CCH, 48, 49, (C) Rh(Phy), Cl+ C,H, +H, —> (PPh;) .RhCI(n?— CoH4) 50. (a) In lanthanides, as the atomic number increases, size of lanthanide ion (La**) decreases. A smaller lanthanide ion forms a stable complex with o-hydroxy isobutyrate ion, Hence, a Lu'*-o-hydroxy isobutyrate complex ion ‘comes out first and Eu comes out ast. the order is Lu > Yb* > Dy* > Eu*42 | Chapterwise GATE Solved Papers 51. (a) The hydration energy of transition metals increases with increase in atomic number and decrease in size. But for Mn (d°) ts value is less. So, for the given metals the correct order is Mn [Co(NHs) s(H 01)?" + [CrCKH,0)5]* follows inner sphere mechanism because it involves exchange of ligand. While reaction , FFe(CN)g]*" + [Mo(CN),]> — [Fe(CN),]> + [Mo(CN),]*~ follows outer sphere mechanism because it involves only transfer of charge. 53. (a) Ni(CO), show L cis [PtCl, (NH,)9] (NH, ligand mainly gives cis product.) 55, (d) Zeise's salt is [PtCl(n?~CyH,] 56. (b) In Wacker process of conversion of acetylene into acetaldehyde palladium(ll) chloride [PdCl,]”° is used as catalyst. 57. (b) Reduction of Mn,(CO),p gives the manganese pent carbonyl anion Mng(CO)yy + 2Na~> 2NafMn{CO) 5] CH,COIMn(CO), 5B. (c) W(CO), + MeLi —> [W(CO) 5(COCHS)] Li (CO), W=C\MeJOMe 59. (d) Besides Fe, the other metal involved in dioxygen transport is Cu. axcoa > s (6) John-Teller distortion is found in the complexes of util), Low-spin Fellt, Till) as these contain asymmetric d-electrons. (@) [ColNH,)](H,0) CI] Br, — [Co(NH,) ,(H,0) Cl} + 2Br- [Co(NH,) Br] Cl-H,0—*[Co(NH,),8r]° +Cl +H,0 61. Since, the above two complexes give different ions on ionization, so they exhibit ionization isom Transition Elements 62. (b) [Co(CO} 4] is compound with 17 electrons, Since, it hhas one electron less than the 16 electrons so its isolobal with CH, which has one electron less than octet, 63, (b) Electrons in Fsubshell does not screen the nuclear charge effectively, so the nuclear charge increases. Which results in decreased size and increased electronic repulsion. So, chances of interaction with the ligands becomes less and hence, LFSE are small 64. (a) [Ce(NO,)]* has icosahedral structure. Other given complexes have eight coordination number and thus, have square antirismatic structure 65. (d) Any factor which increases the electron charge density in x* orbital ofthe ligated CO, would decrease the C—O bond order and also the vibrational frequency of C—O bond. The presence of positive charge on metal carbonyl would resist the flow of the metal electron charge to x" orbitals of CO: Thus, CO in metal carbonyl cation would absorb at a higher frequency. The value of M—C stretching frequency for the given complexes is [V(CO),}“' = 1859 cm” [Cr(CO),] = 2000 cm" [Mn(CO},]* = 2090 cn 66. (a) The complex ion [Cu(NH,},]* has octahedral geometry, 67. (a) Since, the metal in [Cu(NH,),]”* contains only one unpaired electron, spin multiplicity 2-is written above the free ion energy configuration. The ground state energy level 2E, contains two degenerate energy levels corresponding t6 the orbital arrangements 8,02, db, andth, d!,d_,2. The excited state 2 oe_y 2 ay energy levels contains three degenerate energy levels from three degenerate orbital arrangements Cr di, diz dy eg and a, dled ef. Thus, the absorption band is assigned to only one 2E_ > "Tyg transition 68. (a) trans{PtCl,(NH,\PPh;)] is prepared by the reaction of [PtCl,]" with PPh, followed by the reaction with NH. This is because both of rans effect is PPh, > Cl" > NH; (ranse‘fect is the ability of a group to direct an incoming group to occupy the position trans to that group)00960009 000 0-— - a & e@ocecorooonsooos Transition Elements . a PPhy I - | aie = cata =r a a PPh," \ =Nu/cLpr*—cl =r i NH, transform 69. (b) In [FeF,]*, iron is present as Fe™* Fe = [ad 3d? ad Ai} 4]4 44/4 Ithas symmetrical orbital, so no transition occurs. In {Cok}, cobalt is present as Co** Co = [Ar] 3d® oa? A }H [1% Because of asymmetric geometry one transition OTyg > Eg) occurs, Thus, its electronic spectrum shows one absorption band. 70. () The reaction, [CoCINHs)5]* +[CrIH,0),]** —> [CoH OMNH;) 5]* + [CrCl04,0),)* involves the following steps : 1,(CrH,0),]"* + [Co(NH;) ,C)* 5 [(H,0), Cr—Cl-Co(NH,),]* +H,0 II. [[H,0) 5 Cr—Cl—Co(NH)]** ie ICr(H,0),Cl]* + [Co(NH,) ,(H,0)]" Transfer of electrons is involved so the reaction will follow inner sphere mechanism, In this reaction CI” is bounded with both the metals in the electron transfer transition state, So, it acts 2s the Chemistry | 43 bridging ligand. ~ 71.10 ViCgH)} (5 +12-1=16) has zero unpaired electron while CriCgH,)$ (6 +12-1=17) has one Unpaired electron. 72. (@) Nitrogenase enzyme has Mo and Fe metals. 73. (a) CrOf has a tendency to get reduced (oxidize others). So, it acts as strong oxidizing agent. 74. (c) Number of metal-metal bonds are calculated as InFe(COlp, 2xm+Axn+2XL= Ato. of nearest inert gas x n 2X x+26X242%9=36x2 2x52 418=72 InCop(CO),, 2xx+I7XI+2XB=36X2 In[Re,Cly]?- 2xm475x24+2%x8-2 m InRuy(CO),, 2xm444x3+2x12=54x3 6 m=2=3 Thus, Re,Clg]™ has four metal-metal bonds as 2 ‘Structure of [Re,Cly]™ 75. (a) = (nin +2) = 4.9 nea Fe® in [Fe(H,O),1"*, has 4 unpaired electrons. Thus, its magnetic moment is 4.9 BM.Chemical and Ionic Equilibrium Syllabus Chemical and tonic Equilbrium Kinetic theory of gases, ideal and non-iea! solutions, phase transformation : phase rule and phase diagram. One, two and three component systems, chemicel equilbrium, response of chemical equilibrium to temperature and pressure, coligative properties, GATE 2011 (1 Mark Questions) ¥ Solution Points 1. The freezing point constant for water is 1.86 K(mol/kg)~'. The freezing point ‘when 0.01 mol glucose is added to 1 kg water is (@) 1.86K )-186K —) 0.0186K —() -0.0186K 2, On the pressure-temperature diagram for a one-component system, the point where the solidliquid and the liquictgas curves intersect is (a) triple point (b) critical point S (c) melting point (@) boiling point “ . ! 4 é 3 A Temperate < ‘According to the Ehrenfest classification of phase transition the aboye diagram refers to ie (a) zeroth order phase transition 6) fist order phase transition (©) second order phase transition (d) 2. transition GATE 2010 4. For the pair of reactions given below, (0 Ny(@) + 3Hyle) —= INH) iD jm + 3a) = NH If at a particular temperature, K,y and Kp are the equilibrium constants for reactions (i) and (i respectively then,o-0-0-~ @ ¢ ) © ¢ ¢ © © © e 6 e 6 © Se S © Chemical and tonic Equitibrium fa) Ky =2k, UY Ky = Kp, (©) 2Kp, = Kp, (Kp, = Kos 5. For an ideal gas, (2) @p/ANyAT!AN,@VAp), =O (b) @p/BNy @T/AV,(@VBpiy= -1 (0 @pfaMyLBTIAV,AVMp), = +1 ) @plAN (ATION V/OP), = +2 GATE 2009 6. The number of degrees of freedom of a system consisting of solid sucrose in equilibrium with an aqueous sotution of sucrose is é @o 1 2 @3 GATE 2008 C-o) , 7. Mfa gas obeys equation of state pV ~ nb) = nRT, the ratio —* —"_ ig (Cy ~ Cider (@)>1 (bj Byttig > BsHy > Byghtyg (6) BH, =BgHyp > BsHy = Broth, (0 BigHy, > Bote > ByHyc > BM, () BgHy > ByHyg > BH, > BycHy, GATE 2006 9. As per the kinetic theory of ideal gases, which of the following statements is not correct? {@) Gas particles have mass but no volume {b} Panicle are in @ Brownian motion between collisions (€) During the collision, the system does not lose energy (d) Particles exert same force per unit area on all sides ofthe container GATE 2005 10. The triple point for water is (a) unique i (b) depends on p but is independent of T o (0. depends on T but is independent of p (6) depends on bothyp and T GATE 2003 11, The intemal pressure of a van der Waals’ gas is (a) independent of the molar volume (b) inversely proportional to the molar volume {c) inversely proportional to square of the molar volume {€) directly proportional tothe moar volume Chemistry | 45 ¥ Solution Points€ 46 | Chapterwise GATE Solved Papers Chemical and lonic Equilibrium GATE 2011 (2 Marks Questions) ¥ Solution Points 12. For 1 mol of a monoatomic ideal gas, the relation between pressure (p), volume (V) and average molecular kinetic energy @ is Nae Nat Nae ty p= Nae aay © pay Ine 2N, ) p= at @ p= Oey Pe ove GATE 2009 13, Among the following, the equilibrium which isnot affected by an increase in pressure is (a) 250,(g) — 250, (g) + 0,(2) ) Hyg) +1(9 == 2HI@) (0 Cs) +H,0%@) —= COG) + Hx(@) (d) 3Feld + 4H,0(g) — Fe,04(9 + 4Hy(g) s GATE 2007 ; : 14. The number of degrees of freedom for a system consisting of NaCl(s), Na*(aq) © and Cl" (aq) at equilibrium is a @2 (b) 3 ‘i 4 id) 5 15. In the mixture obtained by mixing 25.0 ml. x1.2 x10" MMnCl, and 35,0 mL.of6.0 x 10 MCI solution, the concentration (M}.afMn*, K* and . © CI” ions respectively are fa) 6.010, 3.0 x10, 1.5 x10 - e (b) 6.0 x10, 3.0 x10, 9 x10 & {0 5.0.x10%, 3.5 x10, 13.5 x10 (A) 5.010, 3.5 x10, 8.5 x10 GATE 2000 16. An aqueous solution containing m moles of non-volatile solute freezes at 0.186°C. The elevation in the boiling point of the same aqueous solution (Ky = 1.86%, Ky =0.512°) would be (a) 0.186 (b) 0.512 (9 0.0512 @ 0.51/86 17. Under the equilibrium conditions forthe reaction, is) + COg(g) + 2CO(g), te total pressure is 12 atm. The value of K,, is @ 16 ib) 05 2 (@ 32 18. The pH of buffer solution containing 4 x 10™ and 0.4 moles of acetic acid (PK, = 4.76) and sodium acetate respectively will be (a) 6.76 (b) 4.76 (0 2.76 @) 0.76LOO © a ADODOOOD OD € Q Q @e 00 0 6 Answers with Explanations 1. (d) We know that depression in freezing point, AT, =iK;-m Glucose is a non-electrolyte, so. Given, K, =1.86 K (molkg)* Moles of solute _ 0.01 Mass of solvent (in kg) 1 AT; =11.86 0.01 = 0.0186 K T, =0 ~ 0.0186 = -0.0186 K Molality m 2. (a) Triple point isthe point on the p-T diagram for one Component system at which the solidiquid and the Tiquid-gas curves intersect. In other words, at this point all the three phases (solid, liquid and vapour) can coexist in equilibrium. =) (& | 3.¢){F2] -(#2] oy, -Van= An = , vee) ™ According to Ehrenfest classification a transition for which the first derivative ofthe chemical potential with respect to temperature is discontinuous is classified as first oder phase transition, 7 — 7 (= chemical potential and V = volume) 4. (b) Koy =P Pry “Pip Pring 2 2 R= Pie ti) Pr; "Ph, Dividing Ea. (i by Eq. (, Kp 5. (a) For an ideal gas, ‘At constant volume PB constant @) Similarly, (#) =0and 4) Vp Py Thus, @p/@Ny BTV), (BV/Gp), = 0 6. (@) Since, solid sucrose is also present in the solution, so there will be two phases (P = 2). There will be two ‘components. So, according to phase rule FaC-P42 Fe2-242 Fe2 7. (0) For ideal gas, pV = RT Change in enthalpy (AH) can be given by AH = AE + paV For 1 mol of an ideal gas, pV, =RT, and pV, =RT, PWV, -Vy)= RT, ~1) or pAV = RAT Hence, AH = AE + RAT or aH aE ik at aT If AH and AE are infinitely small, we have or €,=Cy4R or C,~Gy=R In case of real gas, volume is Vb and thus, the gas equation becomes p(V — nb) = RT For 1 mol of real gas, pt, ~ b)=RT, and PAV) ~ B)= RT pl, ~ V4) = RIT, ~ T,) pAV=RAT yp ~Cy=R ov) (C= Cis 8. (0 Bronsted acidity of boron hydride follows the order ByoHy, > BsHy > B4Hyo > Boy This is because acidity increases with increase in the size of borane. In larger borane, the charge formed ‘upon deprotonation can be better delocalised over a large anion with many boron atoms than over a small one,48 | .Chapterwise GATE Solved Papers 9. (d) According to kinetic theory of gases, (0. Gases are made up of small units, called atom or molecules. Volume of individual atom or molecule is considered negligible. (i) Gas molecules are’always in rapid random motion colliding with each other and with the wall of container, So, they do not exert same force per unit area (i.e, pressure) on all sides of the container. (ii The collisions among the gas molecules are perfectly elastic i.e, involves no loss of energy. 10. (¢) Triple point of water exist a temperature 0,0098°C and 4.58 mm pressure. In case of any. change in temperature and pressure, the triple point vanishes. 11. (0 Internal pressure, ry = (2) 1 wv, au -(2) ds + (2) wv as), a) On dividing by dV, we get aU (as) WU) 7.25) _ (a), (av), -? ap a, =1(2) - " (i), : ne a (for ideal gas) In case of van der Waals’ gas, Thus, internal pressure varies inversely with the square of molar volume. 12. (©) Kinetic gas equation is ee pV = tmNu ug Chemicat and tonic Equilibrium 13. (d) 3Fe(s) + 4H,O(g) —* Fe, 0, (9) + 4H, (8) In this equation, the number of moles of gaseous reactants and products are same. So, it will not be x affected by change in pressure. € 14, (b) The given system has two phases solid NaCland aqueous solution and three components, ie,, NaCI9, Na*(aq) CI” (aq). @ F=C-P42 Fe3-242=3 & 15. (c) For MnCl, solution, the initial volume was 25 mL. After addition of 35 mL KCI solution the solution is difuted by to 60 mL, so the concentration of Ma* ion 25 will become = 1.2 x 107? x In case of KCI solution, the concentration of Kis 35 = 6x10 X= =3.5 x10 60 MnCl, on ionization will give 2CI” ions and KCI will give one Cl" ion per molecule so the concentration of Ch =2x5 x10 +3.5 x10 = 13.5 x10" oF 1.35 x10 16. (9 We know that, m = AU = 9-186 _ 9 1 Ky, 1.86 AT, =K, xm AT, =0.512 x01 AT, = 0.0512°C 17. (@) At equilibrium, the pressure of CO, is p. In the reaction CO,(g) + C9 200 Presueat pO 2» S equilsiam or p+2p=12 p=4 Partial pressure of CO, = 4 Partial pressure of CO = 2x 4=8 2 @e Poo) 8 16 eo) 4 {salt} 18. (@)pH= pk, + log ==" pH = pK, +108 = 4.76 + lo 8 x10 6 .76 +\0gl00 = 4.76 +2 @ =6.76 LOO 9 © 9 _6_ Electrochemistry Electrochemistry Debye-Huckel Theory : Thermodynamics of electrochemical cells; Standard electrode potentials; [ees applications, corrosion and energy conversion, Acti coefficient, fugacity and fugacity coefficient. GATE 2010 (1 Mark Questions) 1. The standard reduction potentials at 296 K for single electrodes are given below. Za" Zn | 0.76 From this we can infer that (a) Zn can reduce both Mg** and Fe’* (b) Fe can reduce both Mg”* and Zn** (0) Mg can reduce both Zn** and Fe** (@) Mgcan reduce Zn”* but not Fe” GATE 2009 2. According to the Debye-Hucke limiting law, ifthe concentration ofa dilute aqueous solution of KCI is increased 4-fld, the value of In, (7, isthe molar mean ionic activity coefficient) will (2) decrease by a factor of 2 (b) increase by a factor of 2 (©) decrease by a factor of 4 (@) increase by a factor of 4 GATE 2006 3, Given the standard potential for the following half-cell reaction at 298 K, Cutlaq) +e —> Cul; FP =0.52V Cu?*(aq) +e” —> Cut(aq); F = 0.16 V y Solution Points50 | Chapterwise GATE Solved Papers Calculate the AG? (k)) for the reaction, [2Cu* (aq) —> Culs + Cu?"] (@) 34.740 (o) -65.720 (9 ~69.480 (@) 131.440 GATE 2002 4, The Nemst equation for the reaction, A" +2e” — B, in terms of the free energy change is (@) AG= AG + 2.30387 log 4 tb) AG=AG" ~ 2,303 RT log ia) (©) -8G=~AG* +2,303RT log A AG? +2.303R7 los (d) AG @ 7 GATE 2011 (2 Marks Questions) 5. For the concentration cell, M|M* (aq, 0.01 mol /dm) | | M* (aq), 0.1 mol /dm?| M the EMF (6 of the cell a a temperature (7) equals ta 2.30382 (o) -2.30387 F F ° aT ° aT. (0 yay +2303 (8 Egy ~ 23035 6. For a 2 molal aqueous NaCl solution, the mean ionic activity coefficient(y) and the Debye-Huckel Limiting Law constant (A) are related as (a) logy, = VA (b) logy, =-V2A (OY, =10* (@) y, =10% 7. The activity of water at 11 bar and 298 K is fa) 1.101 (o) 1.007 (c) 0.998 (d) 0.898 GATE 2007 8, Given that €° (Fe, Fe) = -0.4 V and E°(Fe*, Fe) = E*(Fe*, Fe**)is (a) 076V to -0.40V (9 -0.76V (@) 0.40 0.44 V, the value of 9. A student recorded a polarogram of 2.0 mM Cd solution and forget to add KCI solution. What type of error do you expect in his results? (a) Only migration curent will be observed (b) Only diffusion current will be observed (©) Both migration current as well as diffusion current will be observed (@) Both catalytic current as well as diffusion current will be observed Electrochemistry + Solution PointsElectrochemistry Chemistry | 51 GATE 2003 ¥ Solution Points 10. For the reaction, Hg,Cla() + Hp(@) ~> 2Hg(liq) + 2HCllaq), the correct representation of the cell and the thermodynamic properties AG, AM and AS at 298 K respectively, are (Given : Easy = 0.2684 V and temperature coefficient = 3 x 10“ VK™!) (a) PHH(g, Tat) | HCl(a@|Hg2Cl(g)|Hg(liq) AG = -51.8W mol", AH = -69 Kmol”, AS =~58 JK™' mol (b) Pt]Ho(g, Tatm)| HClag)| Hg, Cl, (g)| Hetlig) AG =~25.9 kj mol", AH = -34.5 kJ mol”, AS = ~29 JK' mol"! (c) Ha dig)| Hg2Cla(e)| HCKaq)|Ha(g, 1atm)|Pt AG =~51.8k{ mol", AH = -69K) mol, AS =~58 JK~ mol" (@) Hgtigh Hg, Cl, (| HClaq)|Hy(g, 1 atm) |Pt AG =51.8 klmol”, AH = 69 kimol”, AS = 58 JK" motAnswers with Explanations 1. (C) Metals with lower SRP can displace the metal with M+M* (0.1) —>M*(0.01)+M hhigher SRP from their solutions. Mg with lower SRP (2.34 can reduce both Zn**(~0.76) and Fe®*(-0.44. 2:303RT gM Inon, Finf= B° 2, (@) Debye-Huckel equation i nf Moy “ore ‘ iz ah = po ~ 2303R7 |, 0.01) inty,) =~ AZP Vi Dre ay ‘constant depends upon the solvent py FE al harge number of ionic species i aairh gue * Eu 1 = ionic strength =0 log(0.1) Let the concentration of ions is Cin dilute solution. _-2303kT lay, =- AVE =a tere deKe}xay? edie) x ey? = 4 230387 2 2 F 1 = xCxI4 EXC #12] 6.) logy, = Az2vi 2 @ When concentration is increased four times, f= 3B xa? 42x04 : = & c=aC F ology, == Atl)? (2) =~ AZ =- 2A ' (40) XO)? + (40) x ON? = AC é 2 2 7. (b) ALNTP, concentration of water = 55.5 mol/L (Iny,)2 =- AVAC = - 2-AVE = 2 x Ing, n=CRT © Thus, Iny, is decreased by a factor of 2. x ® 7 3. (a) Cut +e” —> Cu; F° =0.52V wk, CRE & = 1% 96500 «0.52... am : ; 1M Gx298 55.5273 es or Cut Cu? +07; == 0.16 V a © AG) ==1% 96500 x (-0.16)..(i) & On adding Eqs. () and (i), we get 2Cu* —> Cu+ Cu", =10.07 % AG=AG, +AG; = 10.07 100 in percentage) (- 96500 x 0.52) + (96500 0.16) 1000 = 96500 (-0.52 + 0.16) =1.007 = (96500 x 0.36) 8. (a)Fe™ +3e° — Fe; E=-04V 34,740 |= ~34.740K) AG =-3xF x04 4. (a) Nemst equation for the reaction, A + 2e” ~ B, in $0.12 F r terms of the free energy change is a Fe* +2e” —> Fe;E° =-0.44V ia (On inverting, we get Fe—oFe™ +20; =+0.44V 5. a) Forthe cell, 3 te 2xF x04 (M|M*(aq, 0.01 mol dm™)|| M* (aq, 0.1 moVdm?)|M the cell reaction is 0.88 F Ai) AG=AC* + 2.303RT log. @ & @ ©Electrochemistry On adding Eqs. fi) and (i), we get Fe* +e” —>Fe*; AG =AG; + AG; [+ 0.12 F+(-0.88F)] O76F AC? = — nF ES = O.76F = -1X FX Egy Eva =+0.76V 9. (d) KCI gives K* ion to form a counter ion that shields the negative charge on the drop and prevents metal ion reduction In the presence of KCI only diffusion curtem is observed, Otherwise both migration current as well as diffusion current will be observed. 10. (a) AG = —nFE A 2 x 96500 x 0.2684 (Here, n = 2 as two electrons are taking part in the cell reaction.) AG = ~ 51801.2 Jmol = ~ 51.8 ko!” ‘We know that AG= AH - TAS ae «(5 (where, | = temperature coefficient) a), Chemistry | 53 and AG=—FEgy ~AFE gy = BH — [ nF &y BH = —nFE gy —nFT| () ar), fer] =~ 2.x 96500 (0.2684 +298 x 3x10") 69.055) AS ==nF () aT), 2 x 96500 x3 x10 6x 9.65 57.9 JK" mot The oxidation and reduction half reactions are as At cathode 2Hg} +2e° —» 2Hg (Reduction) H;— 2H" +e” (Oxidation) At anode So, the celhis represented as Pt|H, (atm) | HClad) || He2Cl, (@) | Heli)2 € Chemical Kinetics & Syllabus Chemical Kinetics Rates of chemical reactions, temperature dependence of chemical reactions; slomentary, consecutive and parallel reactions; steady state approximation; thesis of reaction rates-colision and transition stato theory, relaxation kinetics, Kinetics of photochemical reactions and free radical polymerization, Homogeneous. catalysis, adsorption isotherms and heterogeneous catalysis. GATE 2011 (1 Mark Questions) + Solution Points 1. Fora given first order reaction, the reactant reduces to 1/4th its initial value in € 10 min. The rate constant of the reaction is 7 (@) 0.1386 min”? (b) 0.0693 min e (©) 0.1386 mol min (@) 0.0693 mol "min" Statement for Linked Answer Questions 2 and 3 The decomposition of ozone to oxygen, 203(g) — 30,(8) occurs by the mechanism (i) Mg) + Os) > 0,(6)+ O@ + MQ), E,, Gi) O,(g) + 01g) + Mig) —2-> Mig) + Oy), Es, {ii O(@) + 0,6) 220,18), E, ‘where, Mis the catalyst molecule. ’arerate constants and, isthe activation energy for the elementary step. 2. Under the steady state approximation for the intermediates, the cate of decomposition of ozone, 210, ig fa) —2ktksIO,}*M to) —2ks1037°14 KOM] + & (05) KOH) - KO] Ps (9 —hkalOs1 w 2ksko{O,P'(M) & K,{0,11M + k(0,] K,{021IMl - 15105) 6© ° Chemical Kinetics 3. Assuming ky[O3] >> k;{0,IM, the activation enesgy of the overall reaction is E,, Eas € a OE, +E, ~ Ea, @ Ob, @&, @| GATE 2009 4. For the reaction shown below, ; << the value of k, is 1x 107s". If the reaction starts from X, the ratio of the concentrations of Y and Z at any given time during the caurse ofthe reaction is found to be = +, The value of kis mq 4 (@) 1x 10457 (0) 2.5 x10% st (©) 4x10%s" @ 35x10%s™ GATE 2008 5. ALT = 300K, the thermal energy ke7] in cm” is approximately (a) 20000 (b) 8000 (© 5000 (@) 200 6. For the reaction, 2X; —=*3X,, the rate of formation of X, is @ 3-04 ido tl a) “to fd Jb) 2a) ie 7. In a homogeneous catalytic reaction, 1.0 M of a substrate band 1.0 HM of a ‘catalyst yields 1.0 mM of a product in 10s. The turnover frequency (TOF) of the reaction (5°) is fa) 107 10? (9) 10° (a) 10° GATE 2007 B. The value of the rate constant for the gas phase reaction, 2NO, +F; —> 2NO,F is 38 dm? mol” s~ at 300K. The onder of the reaction is @0 1 o 3 GATE 2005 9. A reaction follows second order rate law, — ats = KAP, if {@)_a plot of [A] versus isa straight ine {$o¥ a plot of 1A] versus tis a straight line Chemistry | 55 ¥ Solution Points56 | Chapterwise GATE Solved Papers (9a plot of fat versus isa straight line (d) a plot of e!! versus t is a straight line GATE 2003 10, Ina consecutive first order reaction, (where k, and k are the respective rate constants) species B has transient existence. Therefore, 7: @ k= ky (b) k, = 2k, (ky >> ky @) iy 7 ‘The activation energy of decomposition for this compound at 300 K is, 4a 24 kcal/mol (b) 12 kcal/mol (©) 24 calimol (@) 12 callmol GATE 2009 12, The halflife ty) for the hydrolysis of an ester varies with the initial concentration ofthe reactant ({E]g) 2s follows : (foftd mol/L 5.0 4.0 3.0 tls 240-300 400 The order of the reaction is f @o 1 eo? @ 3 13, The fuarescence life time of a molecule in solution is 10ns. If the fluorescence quantum yield is 0.1, the rate constant of fluorescence decay is (@) 1x10°s tb) tx 108s? ( 1x107s* (@) 9x107s" GATE 2007 14, For the reaction, P+ Q +R S, experimental data for the measured initial rates is given below : The order of the reaction with respect to P, Q and R respectivel Chemical Kinetics ¥ Solution Pointseeeeose ef eonoe oe eo: Chemical Kinetics (@) 2,21 ) 2,1,2 211 @ 1,1,2 15, Sucrose is converted to a mixture of glucose and fructose in a pseudo first order process under alkaline conditions. The reaction has a halflife of 28.4 min. The time required for the reduction of a 8.0 mM sample of sucrose to 1.0 mMis (@) 56.8min —) 1704 min = (85.2min (4) 227.2 min 16. The reaction, 2NO(@) + Ox(g) —> 2NO,(g) proceeds via the following steps NO +NO—S5 N,O N,O, 4 NO+NO N,O, +O, aren NO, +NO, The rate of this reaction is equal to @) 2kyINO} [04] (b) AK kyINO}OAK, + ky[Oz)) {G1 2kpNOP103] (@) K,{NO7{0,) GATE 2006 17. 1 g of Sr gets converted to 0.953 g after 2 yr. The halflife of °°Sr, and-the amount of ®Sr remaining after 5 yr are (@) 1.44 yr and 0.916 g () 57.6 yrand 0.75 g 4) 28.8 yr and 0.887 g (d) 100 yr and 0.982 g 4 18. Consider an exothermic reaction, A <=! As the temperature increases (@) ky ky and klk. increase (b) k; increases, k.; decreases and kyl. increases (0 ky ky and kyk. decrease (@) ky and k_, decrease and ky/k_ increases 19. A reaction proceeds through the formation of an intermediate 8 in a unimolecular reaction As pyc The integrated rate law for this reaction is @) [A= [Alpe (b) [Al= [Aly (eS ~ e™) = (Alo, kee Ene @aR=5 (- (d) [A= [Alp + e! - eh) Chemistry | 57 v Solution Points58 | Chapterwise GATE Solved Papers 20. Ifk, >> ky, then concentration versus ime plot forthe reaction is g\a a Sia e 5 : + @ 8 & § 6 8 ¢ 6 Time Tine a oe 5 g 8 o§ @ § g . 8 c | Time Time | | GATE 2003 | | 21. H, and Br, react to give HBr by the following steps | | 4 Bry + M—3 28r+ Maso = eae k, Br +H, —25HBr + Hislow) H+ Bry 2s HBr + Br (fast The probable rate law for the above sequence is (@) Rate = k,(K)"? [Hy] [Br)]'? ——(b) Rate = kp (H] Brg] (6) Rate = ky (k,)""(H2) [Br ]"? —(d) Rate= ky (K) {Ha} —Bry]"” GATE 2002 | 22. The half-life of a first order reaction varies with temperature according to (@) Inty = i (b) Inty, &T © ty © UT? (d) ty, &T? GATE 2000 } 23, The halflife time for a reaction at initial concentrations of are 200 s and 50 s respectively. The order of the reaction is g) 0 4 Ad 2 @3 and 0.4mot* Chemical Kinetics y Solution Points€ @02000 6 6 6 ° Chemical Kinetics Chemistry | 59 Answers with Explanations 1. (@) For the firs order reaction, 2303, a ka log Given, t= 10min 1 = 0.1386 min™ 2, (a) From the given mechanism, FOS 44 [04] + 10} 04] IM -Ky{OH10 Ai) 201 — 0 (04) ~bef021 011M (01104) Ali) ‘On applying steady ate approximation for the intermediate, {0 2] [} IM] + ks[0] 10] (M1) [03] 31M) [Op] + ks [03] Putting the value of [O} in equation (i), we get il) kk10,) M10, 0) - KM t0,)4 = 21M [03] +104 __kiktM [07 EM 10,1+ 103) HOt dt ~kykalM"[0] [03] ~ kyksIO31?1M + kyko[O2] IMI?[05] - kyks(M) [0]* KMM[0,] + i105) A{O,] __2ksksIM1 103]? at kpIM] [05] + ks[05] 3. d) When ks[03}>> k,{O,] [M), _ 103], 2kksM [O3}? dt 10) = 2M [05] Let the overall rate constant, k= ky dink _dink, a dt E, _ Fa RT RT? E+E ie, 4, (@) Rate of disappearance of Xis dildt = k(x a + kyl a) =k, +k) e-a) where xis the initial concentration of xand ais decrease in the concentration at an instant, Rate of formation of ¥ = ky(x — a) Rate of formation of Z = k,(x ~ a) The ratio of formation of ¥ and Z is [YA IZ] = kybx — alPkgtx — a) = klk, ie, YYW = kk 1_1x10~ 4k =4x104s7 .(d) ky = Boltzmann constant Value of Boltzmann constant = 0.6950 cm"* /K Thermal energy = ky x T = 0.6950 cm” VK x 300 K = 200cm™ 6. (d) For the reaction, 2Xy —3X, Rate of disepperance of) = = 203) Rate of appearance of X, a) Rate of reaction, 2251 =. SMa} 2dt 3dt IX; __ Rate of appearance of X = [2 Ws) dt60 | Chapterwise GATE Solved Papers Chemical Kinetics . I ky 7 7. (b) Rate, r= HlProduct) a © at Ifk is very low, reactant predominates and if kis high, ~ 1x10" product dominates. 10 Since, B has transient existence, thus, =1x 107 m/s ky>> ky Tuam ove feqency TOR) = 11 Given Ink 5.0 - 12000 where, Q = concentration of catalyst We know that nk = In A - E& @ x10~ m/s aT = ~ 1x10 ms ‘Comparing the two, we have ra ore E,/R=12000 a £, =12000 x 2 = 24.00 kcal/mol 8, (c) We know that litre = dm? 12. (@) Halfife and intial concentration are related as So, the unit of rate constant twa [ees] . Equate it with general expression (mol /L)'~ teh LE (where, n = order of reaction) Lmol"' = (mol/t)""" Therefore, -n or n=2 7 9. (o) Rate= 214 - ae 7 at e@ or ae o oF a Al & On integrating Eq. (), we get idl Further, UA _ tage rue wi t sak ec “ A & Att = 0, A=[Ag] = initial concentration 1 & (Aol , On puting the value of, we get n=2 oan ‘Thus, the reaction is of second order. (A es 13, (€) Rate constant a p= fluorescence quantum yield tad Tluorescence lifetime - Thus, a plot of +6 and t(y) is a straight line [from the OF ayo? st = 5 equation y mn in wich graph of y and x is a “10«10° straight line] 14. (c) Let the rate expression be r = k [F)™IQ"IRI° 10. (d) Consecuting reaction is the reaction in which the i 7 product formed decays further to form new product. salt) a - 8x10 =(0.2"10.51"(0.4 a)80820008 QO AQ ©eeece 6: @eenece Chemical Kinetics Chemistry | 61 Similarly, 17, (hk = 7283 Jog No 3.2x107 =[0.4)"(05)"10.4" ti) eed 1.28 x107 = (0.4)"2"10.4" «id k= 7303 log 1 - 0.0244 : ; : 2 85953 410% =P" DI5"U-O ee tyy = 0.693/k = 0.693/0.0244= 28.79 From Eqs.) and (i, yr 8x10 (zy Nopyp 32x107 04, No 12. ee ne. =01736 From Eqs. i and fi, 268 4 a 736 32x10 -(°3) a fy] = 0.8878 128x107 (2 Te. nel 18, (@) With increase in temperature, the number of collisions having energy higher than the activation From Eqs.) and (iv) ns energy increases. Thus, rate and rate constant both Be) en pave -( 2 3) (24) increases whether the reaction in exothermic or 4x10 0.17 10.25) 1.6 endothermic. oi tfk, and ky increases, their ratio alsa increases. 15, (9 For fist onder action, 19, (a) Rate equation for concentration of Ais 20.693 e-bay a at 0.693 dial dt ong 00244 a 2.303 f a InfA] =~k,t+C Ai) k a-0 Att=0,1Al= [Ad] 2.303 jo, 8 (On putting these values in Eg. (i), we get = 2303 gg 0.0244 8 InfAgl=~k, x0 +C = 85.2 min IntAal bs = InfA] =~ k,t + In[Agl 46, (¢j Reaction, NjO, +0, —°s NO, +NO, Inf in(Aol = kt isthe slowest step, so the rate expression is Rate = kylN,O,110a] “ : oe 20, (b) If ky >> ky all the A present is converted into 8, Since, NO, is an intermediate so its concentration which is slowly used up to form C. So, concentration vs spout be replace from Eq. (i). For that purpose time plot for such reaction is consider reaction NO+NO~5.N,O, Sha 8 N,O. € For this reaction equilibrium constant K, = “N02 5 INO}? 8 IN,O2] = K,(NOV? ii) Tine From Eqs. (i) and (i) Rate = ky K,{NOJ*[O2] 21. (a) In the given mechanism, step (ii) is the rte of ee = 2kINO}"1031 determining step and rate law is@ 62 | Chapterwise GATE Solved Papers Chemical Kinetics @ Rate = 248 _ 5 na aH ol) o (22) etna - fa. at ee RT Since, Br is one of the reactant, its relationship with other of the reactant must be sought, The rapid reaction 100.693 —Inty = Ina ~ 22 in both the directions of step (i) implies the relationship RT @ given below, KBr) = BA Bl = (y/k Br)? Substituting this value in rate expression (i) Rate = ky(k,/k..) (11 * = Knew constant) & Rate = ka(K) tH IB)" e 22. (a) Arthenius equation is, ke Ae isk & E, E Ink=InA- <2 & or Ink=InA~ oe For first order reaction, 2 ke Thus, the order of reaction is 2. Q &6 e é © 6 ° © e © © ® @eeooecdcecoooooen Chemical Thermodynamics ‘Chemical Thermodynamics First law of thermodynamics, heat, energy and work; second law of thermedynamics and | entropy; thd law and absolute entropy, free energy; partial molar quantties. [ere ~ GATE 2011 (ac LW = (), av ws 2. According to conventional transition state theory, for elementary bimolecular (1 Mark Questions) (© -s (@ -v reactions, the molar entropy of activation AS* is (@) positive {b} zeto (C) negative (G) positive for endothermic and negative for exothermic reactions GATE 2010 3. The molar entropy of crystalline CO at absolute zero is, {@) zero (b) -RIn2 (© Rind @) 2RIn2 4, Among W (work), Q thea), U (internal energy) and (entropy) (@) Wand U are path functions but Q and $ are state functions (b) Wand S are path functions but Q and U are state functions, (0) S and Uare path functions but Q and W are state functions (d) Wand Q are path functions but U and $ are state functions GATE 2009 5. Among the following, the system that would require the feast amount of thermal energy to bring its temperature to 80°C is (a) 200 g of water at 40°C (0) 150 g of water at 50°C (©) 100 g of water at 20°C (@) 300 g of water at 30°C ¥ Solution Points64 | Chapterwise GATE Solved Papers 6. Among the following, the reaction that is accompanied by a decrease in the entropy is (2) No(@) + 3Hy(g) — 2NH3(g) (0) gH, Og (9 + 60g(g) —> 6CO(g) + 6H,0(D) (0 PCls() —> PCA(I) + Cote) {d) 2H,O(!) — Hyg) + On(g) GATE 2006 7. The plot that describes a Camot cycle is 5, my @ |_| (b) T y 5 % © @ T oT GATE 2003 8. The rate of evaporation ofa liquid is always faster at a higher temperature because (a) the enthalpy of vaporization is always endothermic (0) the enthalpy of vaporization is always exothermic (@) the enthalpy of vaporization is zero (@) the internal pressure of the liquid is less than that ofthe gas GATE 2002 9. The enthalpy of formation of AgCl is obtained from the enthalpy change from which one of the following process? (a) Ag*(aq) + CI (aq) —> Agcliss Ub) gid +12 Cly(g) —> Agel (6) AgCliy —> Agts) + 1/2 Ciy(g) (@) Agia) + AuCI—> Auls) + AgCli) GATE 2001 10. For an irreversible adiabatic expansion of a perfect gas from volume V; to Vj, the change in entropy of the gas is (2) aR inv) (b) zer0 {@) lessthan zero (@) greater than zero Chemical Thermodynamics y Solution Points SoU >Chemical Thermodynamics GATE 2000 11. The criterion for the spontaneity of a process is f@) 54, >0 ©) Sy, 20 (0 Sg + MS une > 0 8) BS yp AS yyy > 0 12, AH and AE for the reaction, Fe,0,(9) + 3H(g) —+ 2Fet9 + H,O(1) at constant temperature are related as ta) AH = aE (b) aH = AE «RT } (cl GH = AE + 3RT (d) GH = AE ~3RT 6 oe GATE 2011 (2 Marks Questions) 1 Ar (300 K, 1 bat) > 1Ar (200 X, 10 bar} assuming ideal gas behaviour, the ‘change in molar entropy is eo 13, For the process, eo ; (@ -27.57)/K/ mol (b) +27.57)/K/ mol g (©) 24.20 J/K/ mol (@) +24.20J/K/ mol 7 ©) GATE 2010 14. The change in entropy when two moles of argon gas are heated at constant volume from 300 K to 500 K is (@) -12.74]/ KJ mol (b) -6.37]/K/ mot (© 637) /K mol (d) 12.74)/K/ mol GATE 2009 15. Given that standard molar enthalpies of formation of NO\g) and NO(g) are respectively 90.3 kjfmol and 33.2 K/mol the enthalpy change for the reaction 2NOKg} + O,(g) —> 2NO>(g) is @) 16.6) (b) -57.1K) (9-142 (@) 57.1 16, The free energy change (AG) of 1 mole of an idea! gas that is compressed isothermally from 1 atm to 2 atm is (@) RT In2 (b) -2RT (©) -RTIn2 @) 2RT GATE 2005 17. Standard entropy of erysallite carbon monoxide {in kymol) at 0 K is around (@) 0.03 (b) 2.50 () zero (d) 5.76 GATE 2004 18, The criterion for spontaneous change in terms of the state functions is fa) dUsy 20 (b) dary 20 fo yy 26 (@) dG,y <0 © @ 6 6 Ce Gc e @ e eS © @ e Chemistry | 65 y Solution Points66 | Chapterwise GATE Solved Papers GATE 2003 19. For the reaction, No(g) + 3H(g) —> 2NHj(g) compute the entropy change (in /K/mal) for the process and comment on the sign ofthe property. Data | Species NEG) Ne) He) WU /mot 1923 1306 (@) 5° =~37.65 J/K /mol; negative sign in the gaseous species during the reaction (6) AS* = -198.74/K /mok negative sign indicates that there isa decrease in the gaseuus species during the reaction, (€) AS? = ~31.25 J/K /mol; negative sign indicates that there is a decrease in the gaseous species during the reaction. (d) AS° = + 31.25 J/K/mok positive sign indicates that the reaction is spontaneous. icates that there is a decrease 20. For the reaction, 2Clig) — Casi the thermodynamic properties (@) AG, AH and AS are pos (6) AG, OH and AS are negative (0) AG, AH are negative and AS is positive (d) AGis negative and AH, AS are positive 21. The standard free energies of formation of H,S(g) and CdS(s at 1000°C are 49,0 kJ/mol and -127.2 kJhnol respectively. Use these data to predict whether H(g) will reduce Cds (9 to metallic Cd at this temperature. (@) AG=~ 78.2 ki/mol andH reduces CdS (b) AG=~39.1k/mol and H, reduces CdS (0 4G-=0 kyfmoland the reaction is at equilibrium (d) AG= 78.2 kJimol and the reaction is not feasible GATE 2001 22. Choose the correct criterion of spontaneity in terms of the properties of the system alone. @ @S)yy >0 (b) 5,)>0 (2 O5)u,) <0 @ ddzy <0 Chemical Thermodynamics y Solution PointsQOoeSdaraeno ® @eceooocoooeecoeaoeooo Answers with Explanations 1. (a) We know that, Gibbs free energy, G=H -T5 and H=E+pV Es G=E+ pV-T5 On differentiating, we get dG=dé + pdV + Vdp ~ TdS ~ SdT Ai) For an infinitesimal stage ofa reversible process, dq=dé+dW and ds 4 [-W=pdV] Tds = dé + pov i From Eqs. (i and (i), we get dG = dE + pdV + Vdp — dé ~ pdV ~ SAT = Vdp - SdT At constant temperature, dT dG=Vdp | 2. (@) According to conventional transition state theory, for elementary bimolecular reactions, the molar entropy of activation, AS“ is negative because two reactant species come together to form one species. 3. (c) Although according to the third law of thermodynamics ‘entropy of a perfectly crystalline substance is zero at absolute zero. But CO is not a perfectly crystalline substance and can exist in two ways in crystal lattice. c=0 Let the amount of two species is equal. 2NH3(), entropy decreases because number of gaseous molecules decreases. fa) In a Camot cycle there are four processes, two are reversible and two are adiabatic. In the given graphs, graph a satisfies these conditions. (a) At the time of evaporation energy is required to overcome the intermolecular forces between the molecules of liquid. ie, the enthalpy of vaporization is always endothermic. Since, at higher temperature more energy is available, so rate of evaporation is faster at elevated temperature. ). (b) The enthalpy change accompanying the formation 10. W. of one mole of a pure substance in its standard state from the constituent elements in their standard state is called enthalpy of formation. For Ag, standard state is solid and for chlorine, itis gas. Thus, the process that gives the enthalpy of formation of AgClis Agld + ta, (@)— Acs (G1, For irreversible adiabatic expansion of a perfect Bas, Suni = AS yp + AS gue > “ DS sup > — AS sys (0) According to second law of thermodynamics the criterion for spontaneity of a process is MS yp + MS ur > O-