CHEMICAL SCIENCES CSIR-NET & GATE TOPICWISE COMPLETE SOLUTION Vivek C. Badgujar (MSc. Chemistry, CSIR-NET-IRF, SET, GATE) Assistant Professor, Department of Chemistry, Pratap College, Amalner 425401 (MS.) Email : vivekbadgujar@pea.ac.in Harsha} B. Sarat (MSc. Chemistry, UGC-NET-IRF, SET, GATE) Lecturer in Chemistry, Department of Chemistry, Pratap College, Amalner 425401 (MLS.) Email : harshal.sarafS@gmail.com Kirtikumar C. Badgujar (M.Sc. Chemistry, Gold-Medalist, 2008- University topper, CSIR-NET-IRF, SET, GATE, MRSC), Senior CSIR Research Fellow Department of Chemistry, Institute of Chemical sj, Technology (ICT), Mumbai 400019 (M.S.) Email : kirrtti@gmail.com Marshal C. Badgujar (M.Sc. Chemistry, B. SC. Gold-Medalist, 2010- University topper, CSIR-NET-JRF, SET, GATE) ‘Suman’ Chemistry Classes, Amalner 425401 (MLS.) . Himalaya°Publishing House ‘MUMBA! * NEW OELII NAGPUR “BENGALURU * HYDERBAD * CHENNOPAI * PUNE * LUCKNOW /ANMEDABAD " ERNAKULAM * BHUBANESWAR * INDORE * KOLKATA * GUWAHATI© Authors No part of this book shall be reproduced, reprinted or translated for any purpose whatsoever without prior permission of the Publisher in writing Inspite of best efforts taken to present the book without mistakes, some mistakes may have inadvertently crept in. So we do not take any legal responsibility for them. If they are brought to our notice, corrections will be done in the next ec First Edition 2015 Edition : 2016 Published by: Mrs. Meena Pandey ‘ for HIMALAYA PUBLISHING HOUSE PVT. LTD., “Ramdoot’, Dr. Bhalerao Marg, Girgaon, Mumbai - 400 004, Phones: 23860170, 23863863, Fax: 022-23877178 Email: himpub@vsnl.com @ Website: www.himpub.com Branch Offices New Delhi: “Pooja Apartments", 4-B, Murari Lal Street, Ansari Road, Darya Ganj, New Delhi-110 002. Phones: 23270392, 23278631, Fax: 011-23256286 Nagpur _:_Kundanlal Chardak Indust Estate, Ghat Road, Nagpur - 440 018. Phones: 2738731, 3296733 Telefax: 0712-2721216. “Bengaluru: Plot No, 91-33, 2nd Main Road Seshadripuram, Behind Nataraja Theatre, Bengaluru - 60 020. Phones: 08041138821, 9379847017, 8379847006, ‘Hyderabad: No, 3-4-184, Lingampally, Besides Raghavendra Swamy Matham,Kachiguda, Hyderabad - 500 027. Phones: 040-27560041, 27550139, Mobile: 09370579333 Chennai = New-20, Old-59, Thirumalai Pilal Road, T, Nagar, Chennai - 600 017 Mobile: 09380460419, Pune + Fitst Floor, "Laksha" Apartment, No. 627, Menunpura, Shaniwarpeth, (Near Prabhat Theatre), Pune - 411 030.” Phones: 020-24496323, 24496333, Lucknow: House No. 731, Shekhupura Colony, Near 8.0. Convent School, Vikas Nagar, Aligan), Lucknow - 226022. Nob: 09307501549. Ahmedabad: 114, "SHAIL’.1* Floor, Opp. Madhu Sudan Howse, C.G Road, Navrang Pura, ‘Ahmedabad - 380 009, Phone: 079.26560125, Mobile: 0937708847. Ernakulam; 39/176 (New No: 60/251) 1ST Floor Karitkamuri Road,Emakulam, Kochi - 682011, Kerala. Tel: 0484-2378012, 2378016, Mobile: 09344199799 Bhubaneswar : 5 Station Square, Bhubaneswar (Orissa) - 751 001 Phone: 0674-2532129,9338746007, Mobile: 09883055590 Kolkata + 108/4, Beliaghata Main Road, Near ID Hospital, Opp. SBI Bank, Kolkata 700 010, Phone: 033-32440649. Printed at: Goetanjali Press Pvi.Ud,, Nagpur on behalf of H.P.H.Preface The basic principle in writing of this CSIR-NET-GATE book is to create a guiding text for students-'a text which represents the material in a way that encourages the students for the logical thinking about what they have leamed theoretically in their bachefors/masters. At present in India, the national leve) competitive examinations such as CS[R-NET- JRF, UGC-SLET (SET), I!T-JAM, TIFR, IISe, BARC, ONGC and DRDO exams are of great ‘importance to start advance career after basic graduation! post graduation studies. These above competitive exams test the in-depth and practical knowledge of various basic concepts. Cracking of any above national competitive examination opens several doors of opportunities in the field of industrial/scientific research and mayloffer excelfent job opportunities in the research as well as teaching field. However, the percentage of qualifying students is varied from the 1-10 %. Hence, an attempt has been made by authors to design the book in such a way that students will become more familiar with the type of conceptual questions that are asked in above said competitive exams. ‘The attempt has been made by us to ensure an error free version, however, if any errors or typos have noticed then we sincerely regret for the same. We would like to hear appreciation, suggestions ard comments from fellow teachers and students to improve the book. The suggestions can be send to email: netgate.badgujar@gmail.com Finally we are greatly thankful to Shri, G. N. Pandey (Director of Himalaya Publishing House, Nagpur) for this opportunity and Mr. Dinesh Dhawane, Area Manager for is invaluable support to bring out this book in time. We sincerely hope that present book will be helpful for Graduate/ Post Graduate students, lecturers and professors throughout the Nation. AuthorsAcknowledgement ‘We (authors) would like to express special thanks to our family who encourage and support in preparation of this book. Also we are greatly thankful to the all faculties! professors and lectures from the Pratap College, Amalner (North Maharashtra University, Jalgaon); especially from the Department of Chemistry for their kind suggestions. We are sincerely thankful to Prof. T. V. Rajale (from Department of Chemistry, Pratap College, ‘Amalner) for their kind assistance in reviewing of this book. Also we are sincerely thankful to Prof. P. M. Yeole (from Department of Chemistry, R. L. College, Parola), Prof. B. M. Bhanage (from Department of Chemistry, Institute of Chemical Technology, Mumbai} and Prof. S. D. Samant (from Department of Ghemistry, Institute of Chemical Technology, Mumbai) for their constant inspiration regarding this activity. We are also thankful to our students and friends for their valuable suggestions. Authors:i i Authors Opinion Welcome, it gives us great pleasure to present/introduce one of the unique book for all of Graduate as well as Post Graduate students from chemical sciences branch those are willing to crack CSIR-UGC-NET-IRF & GATE. This book will also constructive to get ready for prestigious state and national level competitive exams such as UGC-SLET (SET), IIT-JAM, PET, TIFR, liSe, BARC, ONGC and DRDO in Chemistry or Chemical Science related branches. Most common question asked by students is “how should I prepare for this exam?” One of the best and easy method fo crack any ofthese exams ist. ¥ Go through the syllabus and pattern of examination Prepare according to the syliabus Collect the previous question papers Solve the topic wise questions, afier studying and reading that particular topic SS SoS ist not ont improve the confidence level face any exam ‘but also in-depth knowledge of respective fleld/ topic. In this book we make an attempt to provide topic wise questions that are asked from last many question papers of CSIR-NET/ SET/ GATE of Chemical Science branch. We try to cover most of the syllabus topies wise in this book. Questions fom more than 25 topics are included in these books which ate frequently asked in CSIR-NET/ SET/ GATE exams. The previously asked questions are not repeated exactly in the same format. However, previously asked questions are repeated by modifying the questions in a different patter’ format. One of the most essential thing is that, although modified Questions are different, but the concept and logic behind it is nearly same. Hence, if you go through previously solved question papers and prepare a note of frequently asked facts, then it will be very much worthwhile to crack the competitive exams such as CSIR-UGC-NETIRF etc. Now-a-days comparative exam are applied everywhere to screen the suitable candidate, However, the percentage of qualifying, students is varied from 1-10 %. These topic-wise questions bank offer a rich store-house of conceptual questions to check the theory and understanding. In addition to this, the carefully graded challenging ‘questions that are asked in CSIR-NET/ GATE exam bring a special perspective in teaching and learning context. Thus, the present book will be definitely important to students. Furthermore, the book will also ‘be very important for Lecturers/ Professors for Undergraduate and Post Graduate university level teaching to build up a competitive exam aspect in students. - Authors oaAbout the exam........ Precisely talking about the CSIR-NET exam, Council of Scientific and Industrial Research, (CSIR) and University Grant Commission (UGC) jointly conducted CSIR-UGC-NET exam for (j) Junior Research Fellowship (IRF) and (i) Eligibility for Lectureship (LS) in various basic sciences. This exam conducted twice in a year, mostly in month of June & December. The notification for the same is announced most probably in the month of March and September respectively on ‘web address: hitp://esithrdg.res.in/ (website for NET exam). ‘The GATE exam is conducted jointly by the Indian Institute of Science, Bangalore and the seven Indian Institutes of ‘Technology (Bombay, Dethi, Guwahati, Kanpur, Kharagpur, Madras and Roorkee) on behalf of the National Coordination Board- GATE, Department of Higher Education, Ministry of Human Resources Development (MHRD), and Government of India. The notification for the same is announced most probably in the month of September. ‘The new pattern implemented from June 2011 onwards for CSIR-UGC-NET-EXAM of Chemical Science branch involves: A single test paper test having multiple choice questions (MCQs) © It carries maximum of 200 marks. ‘* Itis divided into three parts (A, B & ©). * Itis conducted for duration of 3 hours. Part A: Carries 20 questions. The candidate is required to answer any 15 questions. Each correct answer is awarded with 2 marks. The total marks allocated to this section shall B¢ 30 out of 200. This part will test general aptitude art B: Contains 50 multiple choice questions generally covering the topics given inthe syllabus. A candidate is required to answer any 35 questions and each correct answer is awarded with 2 marks. The total marks allocated to this section shall be 70 out of 200, Part C: Consists of 75 questions. A candidate shall be required to answer any 25 questions, each carrying 4 marks, The ‘maximum marks allocated to this section are 100 out of 200. *Note- There will be negative marking @ 25% for each wrong answer. Part | No. of questions | Tobe attempted _] Marks allotted per question Maximum marks A 20 15 2 30 B 30 35 2 70 c | B 25 4 100 Total Marks- 200 Research Fellowships awarded after clearing CSIR-NET-JRF exam (YEAR “Aasount of fellowships 102 GRF) 25,000 per month +20 % or 30 % HRA + Contingency 35 (GRE) 28,000 per month +20 % or 30 % HRA + ContingencyINDEX 1 Atomic structure and Quantum chemistry 24 2 ‘Valence shell electron pair repulsion theory (VSEPR) 25-31 3 Molecular orbital theory of diatomic molecules 32-35 4 sand p-block elements 36-44 5 Transition/Laner-transition Elements 45-65 6 Bio-inorganic! 66-73 7 ‘Term Symbol and electronic spectroscopy 4-84 8 Organo-metallic Chemistry & catalysis 85~104 9 Borane , Silicates, Isolobal fragments, Cages & Metal Clusters os— 112 10 Inorganic Reaction Mechanism 113-117 uw Point group/Symmetry clement 118~ 126 n Solid state Iia7-134 B Molecular Spectroscopy 135 ~147 4 Aromaticity 148-153 15 Organic Reaction Mechanism:- 154-268 ‘Common Organic Reactions & Reactive intermediates Organic Name Reactions & Rearrangements Reagents in Organic Synthesis Mechanisms of Organic Reactions : Labelling and kinetic isotope effects, Hamett equation, neighbouring group participation. 16 Stereochemistry ~ | 269-29 7 Organic spectroscopy 293-319 18 Pericyelic reaetons 320-340 19 Photochemistry 341-355 20 Heterocyclic Chemistry - 356-367| a ‘ a Book for NET/SLET/GATE in Chemical Sciences : 2 11) The average value of the radius in the 1s state of the hydrogen atom is (a9 is Bohr radius) ta) a {b) 1.52 {2}0.75 a (4) 05 25, 12) The difference in energy levels of n= 2 and n= 1 of a particle-in-a one dimensional box is 6 units of energy in the same units, what is the difference in energy levels of n= 3 and n = 2 for the above system? [une 2013] @4 (b)5 (9 (@) 10 13) The wave function tp of a certain system is the linear combination [une 2013] f 3 = y+ ey » fine f “where 1 and Ws are energy eigen functions with eigen values (non-degenerate) E; and E, respectively. What is the probability that the system energy will be observed to be E,? a fe of at af 14) Calculate the total number of microstates for 6 identical particles with their occupation numbers (1,2, 3) In three states is: {June 2013] @6 (b) 12 (c)60 (729, 15) The hermitian conjugate of operator didx, caled (dl dx), i actually equal to [une 2013] (@) ~aidx (b) aidx (0) i(alax) (a) ~i(didx) 16) A constant of motion is defined by the equation: [June 2013] (a) [H, A]=0 (b) <(H.Al> =0 (co) A=f(H) (AEA 17) The orbital with two radial and two angular nodes is [Dec 2013] (2)3p (by 8 (st (aed 18) The energy of 2s and 2p orbitals is the same for [Dec 2013] fai (b) Li’? (c) Beg” (@)H 19) The number of configurations in the most probable state, according to Boltzmann formula, Is [June 2014] (a) es/xe (b) e~s*9 (c) eo (9) -AG/KeT 20) The commutator of the kinetic energy operator, T, and the momentum operator, P; for the one dimensional case is [une 2014] (ain wine 0 (@) ite 21) For a particle of mass m confined in a box of length L, assume Ax = L. Assume further that Ap(rmin) =

™. Use the uncertainty principle to obtain an estimate of the energy of the particle, The value will be [Dec 2014] aH Beal?) HG mi2) ()#/G2m12) (a) #/2mL?) 22) The exact differential df ofa state function f(xy), among the following is [Dec 2014] (a) xdy (b) ax ~Fay (0) ydx ~ xdy (a) Fax ~ Feay [June 2012]Topic 1 ATOMIC STRUCTURE AND QUANTUM CHEMISTRY Questions with TWO marks 1) The energy levels for cyclobutadiene are a+2f,a a and a-2B. The delocalization energy in this, molecule is [June 2014] (a)0 (b) 4B (c)-8B (d) 4a 2) An operator A is defined as = ~ + x . Which one of the following statements is true? [June 2011] (@) Aisa Hermitian operator (6) Aris an antihermitian operator. (c) Both A At and AtA. are Hermitian operator. (d) AAt is Hermitian, but A‘A. is antihermitian operator. 3) Identify which of the following operators is not hermitiang, [Dec 2011] ad a @ tz ga @x 4) A particle is constrained in one dimensional box of a length 2a with potential V(x) = «0 ; x<-a,x>a and V(x) = 0; a = {b) =? (0) =? (d) Sy = < p> 9) For any operator A tna its adjoint At, the INCORRECT statement is [June 2012] {a)AAt is ahérmitian, (b) AAt + AtAis hermitian {@) A+At hermitian (d) A-At is hermitian 10) For hydrogen-like atom with a nuclear charge Z, the energy of orbital with principal quantum number ‘n’ follows the relation. [dune 2042] a 5 z (ent? (Ex - = ()eyx ~ = ex -5Topic 1:- Atomic structure and Quantum chemistry : 3 Questions with FOUR marks 23) The probability of finding the particle in a one dimensional box of length ‘L’ in the region between L 3k : = and for quantum number n= 1 is 0 [lune 20121 | a et aia 2 (a) (342 (3-2 (2 24) A particle in three dimensional cubic box of a L has energy of 24%. The deyeneracy of the sate is {June 2012] (a2 (b) 3 (6 (a) 25) Using Huckel molecular orbital approximation, the two roots of secular equation of ethene are [dune 2012} (@)a+v2p,a-V26 (at Bia (a+ B,a-B (@a+2p,a-28 26) For H, molecule in the excited state 6,' 6,' the spin part of the triplet state with m, is proportional so [dune 2012} (2) a(1)B(2) (b) fa(13B(2) ~ B(A)a(2)] (2) a(1)a(2) (4) [a(1)B(2) + B(1)a(2)] 1 27) The energy of a harmonic oscillator in its ground state is = fo. According to the virial theorem, the average kinetic (T) and potential (V) energies of the above are [Bec 2012] : ho; : he 2 ho; ve3 fe (T= ho; Ve Z ho Ts 5 has Ves ho T=ho; v= 4h T=2 hoy v= = ho {) T=ho; V= -5 ho (#5 hos Ve 5 28) For the particle-in-a-box problem in (0,L), the value of in the n—» «limit would be {June 2013} @Uls (U3 CLs (ay ua ‘sft (Ry = Rydberg constant) The degeneracy of tho 28) The energy of a hydrogen atom in a state is: state will be [Bec 2012] (a5 (b) 10 (25 (d) 50 30) The energy for a single electron excitation in cyclopropenium cation in Huckel theory is {Dec 2013) @B (b)28 (©) 3B (4B 31) Foran electronic configuration of two non-equivalent x electrons [x', x'] which of the following terms is not possible? [Dec 2013] (a) (b) 8D (0)°A oO 5 32) The spatial part of,the wave function of the atom in its ground staie is 15(1) 18(2). The spin part would be [Sune 2014} (a) of1)B(2) (b) B(1)a(2) Ox [a(1)B(2) + B(1)a(2)]_—(d) # [a(1)B@) ~ B(1)a(2)] 33) Simple Huckel molecular orbital theory [June 2014] (a) considers electron-electron repulsion explicitly. (b) distinguishes cis-butadiene and trans-butadiene (c) disinguishes cis-butadiene and cyclobutadiene (4) has different coulomb integrals for non-equivalent carbons.Book for NET/SLET/CATE in Chemical Sclences:4 34) Consider a particle confined in a cubic box. The degeneracy of the level, that has an energy twice that of the lowest level, is [une 2014] {a3 {b) 1 (o)2 ida 36) if =0.8 gq + 0.4 gels a normalized molecular orbital of a diatomic molecule AB, constructed from: and (¥p which are algo normalized, the overlap between gi and Ya is (June 2014] (ao.1t (0) 0.31 (ast won 36) A particle in a 1-dimensional box of length L is perturbed by a delta function potential , 6(x-L/2), in the middie of the box. The first order energy correction to the ground state will be [Dec 2014} @o {o)4 {Qb/2 (a 2/b (Hint: [2 f()ar-aax = f(a] '37) According to the Huckel theory , the x electron charge on central carbon atom in propenyl cation is {CH.CHCH,)' is (in unit of electronic charge) (Dec 2014] (a) 172 (b) WWE (1 (dj2 38) The number of microstates that are possible, when two particle are distributed in four states such ‘that resutting wave functions are anti-symmetric with respect to exchange of the particle , is ~ . [Dec 2014] (a)16— (b) 12 8 (6 ‘ (Questions from GATE EXAM! ‘Questions with ONE OR TWO marks 38) The set of eigenfunction & sin™ (0 0) 8 not an acceptable wave function for bound system, because [GATE 2005) (2) itis not continuous * (b) itis multivalued (c) itis not normalized (d) all of these 1) The 2s orbital of H-atom has a radial node at 2a because ‘3, is propartional to {GATE 2005} (a) (12+ roy), (0) (2+ Haq) (0) (21a) (a) (2 #i2a) 2) In the Huckel miadel for benzene, the x electronic transitions from the occupied to the unoccupied ‘molecular orbitals do not occur at IGATE 2006] ta) 48 (0) 38 Op (@) 18 2 |} Which of the following pairs of operators commute? IGATE 2006] a da a da and — Sand 425 Los a 8 ae Pay e)x24 ans a (o)x¢and 7 (x? anaTopic 1 Atomic structure and Quantum chemistry : 5 Linked Answer Questions (44 and 45) [GATE 2007] 44) Consider a particle of mass m moving in a one-dimensional box under the potential V=0 for 0) of the particle is h h ( =0 (b)

48) The uncertainty in the momentum (Ap,) of the particle in its lowest energy state is (2)Ap.=0 (©) Ap.=* ape (dpe 48) A particle is confined to a one-dimensional box of length 1 mm. If the length is changed by 10°" m the % change in the ground state energy Is. [GATE 2008] (a)2x104 (b) 2x107 ()2x10® —@o 47) The operation of the commutator [x, d/dx] on a function f(x) is equal to IGATE 2008] (a0 (0) (09) (2-4) (a) x dfidx Common Data Questions [GATE 2008} Common Data for Questions 48 49 and 50: An electron accelerated through a potential difference of ¢ volts impinges on a nickel surface, whose (100) planes have a spacing d = 351.8x10-" m (351.8 pm). 48) The de-Broglie wavelength of the electron is The value of 2./ pm = (a/¢ )"in volts is (a) 1.5x10"* (b) 1.5x10° (c) 6.63x10° (a) 2.5x10 49) The condition for observing diffraction from the nickel surface is “@)h>> 2d (b) As 2d (Asad (dy Azad 50) The minimum value of (V) for the electron to diffract from the (100) planes is (2)3000 (b) 300 ()30 (a3 51) The degeneracy of a quantum particle in a cubic box having energy four times that of the lowest energy is [GATE 2009] (@)3 (0)6 1 (4 '52) The de Broglie wavelength for a He atom travelling at 1000 ms“ (typical speed at room temperature) is IGATE 2009] (@)99.7x10-%m (0) 199.410? m (©) 199-410" (0) 99x10%m '53) An electron of mass ‘m’ confined to a one dimensional box of length ‘bff it makes a radiative ‘Transition from second excited state to the ground state, the frequency of the photon emitted is [GATE 2010] aa os ou os i 54) For eigenfunction W = £ (a) ¥; is normalized and orthogonal to 2 (b) ‘M1 is normalized but orthogonal to > (©) Yhis normalized and orthogonal to (4) Vis neither normalized nor orthogonal to in @) and ¥ & in C=) of a particle in a 1-D box of length b(0.< x 2eX><¥> Ans (d):- Let A= operator and At = Adjoint of A then AAT = ATA a This equation (1) is the condition for hermitian operator. This condition is nat valid for A At is not en herman,Topic 1:- Atomic structure and Quantum chemistry : 9 3 | i 10) Ans {d):- For hydrogen atom, Energy will be E, = 13.6 = 414) Ans (a) In quantum mechanies, Average value of the radius (r) is (= f vnnsende w= | Vj. Pygt ‘Since, dc = r@dr sinddbd Hence Integrating between appropriate limit (= Pedr {*sindd8 "do a alg @ re = 3a = 1520 12) Ans (d}-E, = 2 n= 12,3... Energy dference between n= 3 and a= 2s -@)7] age oe ~ Bma® Here a = 2a,So ae she Sh? = am Gay? ~ Bm(4a?) |ae= seal The difference in energy level of n = 2 and n= + of particle in-box is 6 units ie. AE = E)~ E,=6 AAs AE = By ~ By = (2) — (1)") 2 ima? = Now,n=3-—>n=2 yh AE = [(3)?- Olga 1 : =B-4ae sh? 8ma?= 5x(2) * AE = 10 units Cabat Cade Probability of finding the electron in @q and $ atomic orbitals. [Ca]? and [Ce]? Simitarty, = fue fix. Ws Cay + Cp 2 Probability [C4]? = (6) for By 1 4 414) Ans (c):- Microstate = ~ iy! ng! N= Total number of particies = 6 iy My, Ny = number Of state particle OF (Me, My NI + Microstate = ylnying’ a jaa . _§x5x4x3! ae 2xtx3t Microstate = 60 415) Ans (c)- Operator A = = Its conjugate operator At = i 2 Since At = ATA, ((1) which is the condition for Hermitian operator « += (4) (@ rae) G & ' é —____0 mo gene feey(dy a ; aw ata (YG)=15 > ow) From equation (i) and (ii), we get AMS RR Hence At = i will be conjugate operator of A. 16) Ans (a):- A constant of motion is quantity that is conserved throughout the motion, A quantity is conserved, if (HA) 17) Ans (b):- Orbital with two radial and two angular nodes is 5d, Radial Nodes = (n-/~1) For 5d; (n= 5 &1=2) So, Radial Node: ‘And, Angular Node Book for NET/SLET/GATE in Chemical Sciences :10omic structure and Quantum chemistry : 11 48) Ans (b)}:- Li’? ion has one electron is 1s orbital (ie. hydrogen like atom). in case of H like atom, energy of orbital depends upon the principal quantum number ‘n’ af ie. Eya- = ie Eya- Hence, for 2s and 2p orbital, energy will be the same. 419) Ans (a):-Boltzmann’s equation is a probatilty equation relating the entropy $ of an ideal gas to the quantity W, which is the number of microstate corresponding to a given macrostate. q $= KelnW. qa Here, InW = rs aWs elke | 20) Ans (c):- Commutator => [A,B] = AB~ BA=0 () i eg. [fF -£3 4 @) et vR@ : sits —_____ ® equation (1) =» AB Teh Sener = tm dt 2m ae =0 : Hence, [T,, A] = 0 21) Ans (a):- Given: AP (min) = < p? >¥/? ‘Also, we know that neath? b ae = = SE" os hae 1? 2 Energy otperise= 222 = Es - Toy otrareeS om am By putting value of < p? >, we get Pra * 2 nny ( amie \o rath ~ 2mm? (42)a Book for NET/SLET/GATE in Chemical Sciences: 12 _atath? = muta? _ mht = mi? 22) Ans (d):-f (x,y) = Mdx + Ndy ———_______( for exact differential equation aM. aN ay ax : Here, Given : f(x, y) = jae fey @) Wil satisfy the eq” (2), as By comparing eq” (1) and (3), we get 1 x M=-&N=-> y y Differentiate M with respective to mM. 2(8) ay ay Wy Differentiate N with respective to x. ona ( ) 1 ox ax ax 2) ~~ y? Ox an oy From eq’ (4) and (5), we have aM _ oN ay ox 23) Ans (b):-Probabily of finding particle in 1D Box of length L 2 ac Wy = f sin (=) for 1D,0 (1)? + 2)? + (3)* i 14449 =i4 All the above combination will satisfy Equation (1), hence, total degeneracy 25) Ans (c):-Huckel secular equation for ethene is, bal 3 sE=a+8 + Tworootsarea + Banda —B 26) Ans (d):- For Hz molecule in the excited state "0," spin part of the triplet state with m, = 0 is proportional to fo) B@)+ BA) a0] 28, for m, = 0 triplet state willbe 7 [a (1) B (2) + B (1) a (2)] , 27) Ans (a):~ According to virial theorem for SHO B= KEtPE, ‘As, we know that, for SHO. a) Given “f= £ hw Shy =2xKE phw =2aKE, ak sn aw From equation (1),?.£.= Shw 28) Ans (c):- value of(x*) So O2)H deBook for NET/SLET/GATE in Chemical Sciences : 14 wf Paes) ° ia be = @ f “sin eax =F 28) Ans (c):-For hydrogen atom, energy is given by 2 E, = ~Rusjrwheren = 1,2,3... Degeneracy = n? « Degeneracy = 1? «= Degeneracy of state will be 25. 30) Ans (c):- Cyclopropenium cation ; + t =-6F¥— vy a5 wt — cap A Ho diagram fo jlopropenium cao. =2(@ +28) = 20448 ‘Now, by single electron excitation in cyclopropenium cation in Huckel theory, (+28) + (@-8) Encas)eesti Saat Topic 1: Atomic stsucture and Quantum chemistry: 15 =1o4¢ « Total electron energy will be Ex = Exes) ~ Ences) Ey = (a+ 48) — (2a +B) fx = 38 34) Ans (d):-Forn, mé= 41 IFT oseeelt tH] 2) lol My =2,1,0 So, My =0 Spectroscopic state M, = 1 Spectroscopic State = 1 M, = 2 Spectroscopic State M, = 3 Spectroscopic State For two non-equivalent x electrons M, = 0,1,2butnot3 Hence, °d is not possible. 32) Ans (d):- According to the Pauli Exciusion Principle, the wave function of an electron must be antisymmetric. ke ¥(L2)= -¥2,) Spin wave function can be W spin = a(1)a(2) or B(1)B(2) or {o2)p(2) + a(2)B()] ¥ spin = spin part of wave function, itis symmetrical in nature As, ‘WTotal = Wspace* spin ¥ total is anti symmetrical with electron exchange. W space = special part of wave function (symmetrical in nature) So, spin part will be anti symmetric = place) —B(1)a(2)} 33) Ans (c):- Simple Huckel molecular orbital theory distinguishes cis butadience and cyclobutadiene on the basis of energy. As for cyclobutadiene DE = zero; While for Butadiene DE = 0.472 B 24) Ans (a):- For cubic box, 2 B= Enanyine = (08 +5 +2) > Degeneracy = Ing = ny =n, = 4 Ww = (2+ @24 B=(@) +? + Olga Ne Dy Oy 112 121 211Book for NET/SLET/GATE in Chemical Sciences : 16 ht 6h? E=(0°+@)"+ QS game Hence, for degeneracy = 3, Energy will be double. 35) Ans (b):- Given, Y = 0.8 4 + 0.4 bg Y= Croat Coa By comparing, C, = 0.8, C, = 04 Overiap between db, & bg C2 +C3+2,C,8=1 Putting the values = (0.8) + (0.4)? + 2(0.8)(0.4)S = 1 = 0.64 + 0.16 + 2.(0.32)S =1 + 0.645 = 1-020 - 36) Ans (d):- First order energy correction to the ground state will be B= < Yn |H| Yn > = vf 6-2) vom ¥@)= snes We know that [096 (x-J)v eax =f fim CBe(-9 fit) (Df CBs (De Given: [°, f(x) 6 (x a)dx 37) Ans (c):- Since the 8MO is concentrated on the central carbon atom as most ofthe electron density of the allyl cation is located at C2. Therefore, the positive charge is at C; and C3as (see the resonance structures of the allyl cation). pos fone calculates the electron densities, there is ‘exactly Zero positive charge on the central carbon and exactly one-half unit of positive charge on each of the terminal atoms. As shown in the diagram above, the Contribution to the electron density at a specific atom from a single electron in the BMO is given by the ‘Square of the coefficient of that atom in the BMO % for atoms 1 and 3, & ¥ for atom 2./ The m electron charge on central carbon atom in propeny\ cation = 3 + i electronic density a nm | 38) Ans (d)-Micostate= =F. Given N= 4,r=2 2 4 Microstate = 2121 138) Ane (c)-#(4) = sine) For orthonormal function This function is orthonormal i. both orthogonal and normalized. 40) Ans (8):-Let, £6) = ‘e ve f ¥var= a) SOF Laan Itis not normalized function. Given function is non-contiauous. 2 contribution of electron density. 1 = 1 that is total contribution ofBook for NET/SLET/GATE in Chemical Sciences : 18 e 44) Ans (e)= "tas = 2} (2-2) ro)) AtNode, os Equation (1) => (2-2) = 0 a ei=2 a 2 t= ag = 1 for H-atom wwe 2) 42) Ans (d):- In the Huckel model for benzene, the x electronic transitions from the occupied to the unoccupied molecular orbitals do not occur at 18 43) Ans (b):- Two operator commute if following equation is true. (a) -@Ga)}"0 “Clee rorrgre) So + 2S YoQ__ 2) B. ae om -(SeA@]ro eo is +2: =| YO) = Sve + 2 ¥@____@ By substituting the values of equation (2) and (3) in equation (1), we get ‘equation (1) =» [A,B] = 0 44) Ans (a):-Average mornentum is given by (= [vsmavede lb - a pole 4 i ce Ln fe -Qcwf a(S) =e 7a 4 : Topic 1 Atomic structure and Quantum chemistry :19 a m2 2) ci [ sin) cos( (x Acn®) [ sin(™) cos (Sox se [sn sin") cos (™) dx 45) Ans (b)-The uncertainty in the momentum AP, of particle in its lowest energy state AP, = 2. 46) Ans (a):-% change in energy (=x 100) % change in energy (2x 100) =(2x%x100) —— Given:-a¢ = 10-%&e = 1077 _ 2x10? Ee = ps 100 = 210 aera 7 [A.B] = AB- BA=0 (a ~ a a [AB] FG = ( =f x5 £0) =2FG0) —(2) [B.A)ro9 = [F f| f) = dure) d dx Zora? =xf@)+ f@@)_______@) equation (1) => [A.B] =xF'@) — kf'@) + FO) = xf'@)-— xf'@-F@) 2 [A.B] = -1) 48) Ans (a):- De-Broglie wavelength given by oF Also, EorK.E.= imv? a be m