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For offline, simply dovnload our Educore App once & dovnload the e- books inside the app. Educore App is available for Windows Desktop, 10S & Android Eaycore works best in Desktop, Laptop, 7" & 10° tables ‘Typeset by Disha DTP Team Contact us at support@educoreonline.com for any further Note: This app is not accessible on Mobiles. DISHA PUBLICATION ALL RIGHTS RESERVED © Reserved ‘No part of this publication may be reproduced in any form without prior permission of the publisher. The authorand the ‘Publisher do not take any legal responsibilty for any errors or misrepresentations that might have crept in. We have tried and made our best efforts to provide accurate up-to-date information in this book. For further information about the books from DISHA, Log on to www.dishapublication.com or email to info@dishapublication.com GP_3021Senay sonr Ll. 12. 13. 14. 15. 16. 17. 18. 19. 20. a. 22. JEE Advanced 2017 Solved Paper Brean CHAPTERS BASED ON CLASS 11" SYLLABUS ‘Some Basic Concepts of Chemistry Structure of Atom Classification of Elements and Periodicity in Properties ‘Chemical Bonding and Molecular Structure States of Matter Thermodynamics Equilibrium The s-Block Elements Organic Chemistry — Some Basic Principles & Techniques Hydrocarbons CHAPTERS BASED ON CLASS 12 SYLLABUS The Solid State & Surface Chemistry Solutions Electrochemistry Chemical Kinetics & Nuclear Chemistry General Principles and Processes of Isolation of Elements The p-Block Elements The d- and f-Block Elements & Co-ordination Compounds Haloalkanes and Haloarenes Alcohols, Phenols and Ethers Aldehydes, Ketones and Carboxylic Acids ‘Compounds Containing Nitrogen Carbohydrates, Amino Acids, Polymers & Miscellaneous Match the Following Analytical Chemistry 1-6 7-14 15-18 19-24 25-32 33-40 41-50 51-54 55-68 69-76 77-82 83 - 88 89 - 98 99 - 108 109 - 112 113 - 126 127 - 140 141-144 145 - 152 153 - 168 169 - 180 181 - 188 189 - 192aa BEX) 268 1, Some Basic Concepts of Chemistry 1-16 2. Structure of Atom 17-25 3. Classification of Elements and Periodicity in Properties 26-29 4, Chemical Bonding and Molecular Structure 30-43 5. States of Matter 44-54 6. Thermodynamics 55-64 7. Equilibrium 65-84 8. The s-Block Elements 85 - 88 9. Organic Chemistry — Some Basic Principles & Techniques 89 - 104 10. Hydrocarbons 105 - 117 11, The Solid State & Surface Chemistry 118 - 123, 12. Solutions 124-133, 13. Electrochemistry 134-148, 14. Chemical Kinetics & Nuclear Chemistry 149 - 161 15. General Principles and Processes of Isolation of Elements 162 - 164 16. The p-Block Elements 165 - 180 17. The d- and f-Block Elements & Co-ordination Compounds 181 - 197 18, _Haloalkanes and Haloarenes 198 - 203, 19. Alcohols, Phenols and Ethers 204 - 215 20. Aldehydes, Ketones and Carboxylic Acids 216 - 239 21, Compounds Containing Nitrogen 240 - 253 22. Carbohydrates, Amino Acids, Polymers & Miscellaneous Match the Following 254 - 260 23. Analytical Chemistry 261 - 268 + The chapters have been divided as per the Class 11° & 12 syllabus followed by the NCERT books. Some of the chapters which are spit in the class 11" & 12 syllabus in NCERT have been combined. There might be certain topis/ chapters which are not covered in NCERT but are a part of JEE Advanced/ITJEE syllabus. >_3021ee ar | PAPER-1 Soe ‘This section contains 7 questions. Each question has 4 options (A), (B), (©)and (D). ONE or MORE THAN ONE ofthese four ‘options is (ate) correct. 1. An ideal gas is expanded from (p,. V).;) to (P3. V>.T3) under different conditions, The correct tatement() among the following istare) (A). The work done on the gas is maximum when itis compressed irreversibly from (p. V3) t0 (Pi. V,) against constant pressure p, (B) If the expansion is carried out freely, it is simultaneously both isothermal as well as adiabatic (© The work done by the gas isles when its expanded reversibly fom V; to V; under adiabatic conditions as compared to that when expanded reversibly from YV, 10 V, under isothermal eonditions (D)_Thechange in internal energy of the gas is(i) zero, ifit is expanded reversibly with T = T, and (ii positive, ifitisexpanded reversibly under adiabatic conditions with Ty + Ty 2. Fora solution formed by mixing liquids L and M, the vapour pressure of L. plotted against the mole fraction of M in solution is shown inthe following figure, Here x, and Xyq represent mole fractions of Land M, respectively, in the solution. The correct statement(s) applicable to this system is(are) A Y ww 0 (A). ThepointZ represents vapour pressure of pure liquid ‘Mand Raoult’ law is obeyed from x,=0 t0x,=1 (B) The point represents vapour pressure of pure liquid Land Raoult's law is obeyed when x, -> 1 (©The point represents vapour pressure of pure liquid Mand Raoul’s law is obeyed when x, -> 0 (D) Attractive intermolecular interactions between L-L in pure liquid Land M-M in pure liquid M are stronger than those between L-M when mixed in solution, 3. The correct statement(s) about the oxoacids, HCIO, and HCIO,istare) (A). The central atom in both HCIO, and HICIO is sp? hybridized 8) HCIO, is more acidic than HCIO because of the resonance stabilization ofits anion © CIO, is ormed in the reation between Cl, and 1,0 (D) The conjugate base of HCIO, is weaker base than 1,0 Thecolow ofthe Xp molecules of group 17 element changes gradually from yeliow to violet dow the group. This isdue to (A). Thephysicl state ofX, atroom temperature changes from gas to solid down the group (®) Decrease in ionization energy down the group (©, Decrease in x* ~0* gap down the group {B)_Dezrease in HOMO-LUMO gap down the group Addition of excess aqueous ammonia to pink coloured aqueous solution of MCI; 6H,0(X) and NH,Cl gives an octahedral complex Y in the presence of at. In aqueous solution, complex Y behavesas 1:3 electrolyte. The reaction of X with excess HICI at room temperature results in the formation ofa blue coloured complex Z. The calculated spin only magnetic moment of X and. is 3.87 B.M., whereas itis zer0 for complex Y. Among the following options, which statement()isfare)corret? (A)_ Addition of silver nitrate to ¥ gives only two equivalents ofsilve chloride (8) Thebybridization ofthe central metal ion in Y is sp? ©. Zisatetrahedral complex (D) When XandZare in equilibrium at 0°C, the colour of the solution is pink ‘The IUPAC name(s) ofthe following compound is(are) (A)_{-chloro-4-methylbenzene ®) 4-chlorotoluene (© 4-methyichlorobenzene ©) L-methyi-4-chlorobenzene ‘The correct statement() forthe following addition reactions istare) Ee aprcnc a {Mand N vo oH HG Cth c ayycwc w s+ OntOand Pare identical molecules (B) (Mand O)and (N and P) are two pairs of diastereomers (©) (Mand O)and (N and P) are two pairs ofenantiomers Bromination proceeds through trans-addition in both, the reactions SEs Tt 'S questions. The answer to each question isa SINGLE DIGIT INTEGER ranging ftom 0109, both inclusive, 8. A crystalline solid of a pure substance has a face-centred ‘cubic structure with a cell edge of 400 pm. Ifthe density of ‘the substance in the crystal is 8 gcm3, then the number of atoms present in 256 g ofthe crystal is N * 10°. The value of Nis 9, The conductance of 0.0015 M aqueous solution ofa weak monobasic acid was determined by using a conductivity cell consisting of platinized Pt electrodes. The distance between the electrodes is 120 cm with an area of cross section ‘of I em?, The conductance ofthis solution was found to be 5 x 10°98, The pHof the solution is 4. The value of limiting molar conductivity (AS) ofthis weak monobasic acid in 10. 2, JEE Advanced 2017 Solved Paper ‘aqueous solution is Z 10? em"! mol"! . The value of Z is ‘The sum ofthe number of lone pais of electrons on each central atom inthe following species is [TeBrg}*, [BrF,]*, SNF, and [XeF]- (Atomic numbers: N= 7, F=9, Xe=54) “Among Hp, Hey*, Lip, Bey, By, C;,Np,Oz and F, the number of diamagnetic species is (Atomicnumbers: H= 1, He: N=7,0=8, Among the following, the numberof aromatic compound(s) ‘OAAOO OOCO LD Eocene This section contains 6 questions of MATCHING TYPE, contains two tables each having 3 columnsand 4 rows, Based on each table, there are three questions, Each question has four options (A), (B), (C) and (D) ONLY ONE ofthese four option is correct (Qs. 13-15) : By appropriately matching the information given inthe three columns ofthe following table. ‘The wave function, pm is a mathematical function whose value depends upon spherical polar coordinates (r, 0, 4) of the electron and characterized by the quantum numbersn, land m,. Here's distance from nucleus, 0 iscolatitude and 6 is azimuth. Inthe ‘mathematical functions given inthe table, Zisatomic number and ays Bohr radius ColsmaT Column? Caen 2 {2 2 tse © vam (Ze ° o> © 2sorbiat (®)Oneria nade (© Prbailiy density at mules «1 3 So (a 2} lis) oc! Gi vam <(Z]P re) coso—()Prabatitiy desis maximamat nus % iv) 34,2 orbital (iv) xy-plane isa nodal plane (8) _ Energyneeded to excite electron from n=2 n state ton =4 state is > times the energy needed to excite electron from n=6state state 10 GP_3021CHEMISTRY 13, For the given orbital in Column 1, the only CORRECT ‘combination for any hydrogen-like species is (A) GS) 8 Mine © Mme ©) Undine) 14, For hydrogen atom, the only CORRECT combination is A) OO) 8 WMO@ © Moe) © MWR 15, For He* ion, the only INCORRECT combination is A) OO® ®B) iQ © Mee © HHO) 3 (Qs. 16-18) : By appropriately matching the information given in the three columns of the following table Columns 1, 2 and 3 contain starting materials, reaction conditions, and type of reactions, respectively. ‘Column 1 Column 2 Columns T Toluene @_NaOHBr, (PY Condensation (W) Acetophenone (i) Bry/hv ”—(Q) Carboxylation (Ql) Benzaldchyde i). (CHyCO),O/ (R)_Substitution ‘CH,COOK Phenol (iv) NaOWCO, _(S)_Haloform 16. For the synthesis of benzoie acid, the only CORRECT combination is ) Mae ® aye) © MME ©) a@)R) 17, The only CORRECT combination that gives two different carboxylic acidsis, (a) ae ® wMpeing © ani ©) MOS) 18, The only CORRECT combination in which the reaction proceeds through radical mechanism is (A) ae) ® MO © MéGiiy(R) ) (GIR) PAPER - 2 Faces ‘This section contains 7 questions. Each question has 4 options (A),(B),(©)and (D), ONLY ONE of these four options iscortect, 1. Purewater freezes at273 K and | bar. The addition of 345 ‘of ethanol to 500 gof water changes the freezing point of the solution. Us the freezing point depression constant of waters? K kg mol"! The figures shown below represent plots of vapour pressure (V.P.) versus temperature (T) [molecular weight of ethanol is 46 g mol"!} Among the following, the option representing change in the freezing point is t I 3 = a | Water + Ethanol 270273 TK — ® VPiber —+ 273 KS © VPibar —» © VP lar —* 2. For the followingccell, 214s) [ZnSO,(aq) || CuSO4(aq) | Cuts) when the concentration of Zn? is 10 times the concentration of Cu, the expression for AG (in J mot) is [Fis Faraday constant; R is gas constant; Tis temperature; E*(eall)=1,1V) (LIF (© 2303RT+1.1F (B) 2303RT-22F D) -22F‘The standard state Gibbs free energies of formation of (graphite) and C(diamond) at T = 298 K are -A,G°[C(graphite)]= OKI mot 8,6" [C{diamond)] =2.9 mot? ‘The standard state means thatthe pressure should be I ar, ‘and substance should be pure at a given temperature. The conversion of graphite [C(graphite)] to diamond {C(diamond)] reduces its volume by 2» 10-6 m! mol! If graphite) is converted to C(diamond) iothermally at 1'=298 K, the pressure at which C( graphite iin equlibrium swith C(diamand),is [Useful information: 15= 1 kgm?s-®; 1 Pa= 1 kgm! s%, ar = 105 Pal (A) 14501 bar (B) 58001 bar (© 1450bar (©) 29001 bar Which ofthe following combination will produce H, gas? (A) Fe Metal and cone. HNO; (®) Cumetal and cone. HNO, (©) Znmetal and NOH(aq) (©) Aumetal and NaCN(aq) in the presence of at ‘The order ofthe oxidation state of the phosphorus atom in HPO,, ,POy, HsPO, and 11,P,0, is (A) HyPO;> HPO, > HjPO,> H,P,0, (B) HPO, >H1,PO, > 1,P0,>11,P;0, (©) H;PO,>H,P20, > H;PO;> H,PO, (©) HPO, >11,PO,>11,P,0,>11,P0, ‘The major product of the following reaction is on CQ) a ‘)NaNOp Lore “hao NH, ou ‘cl ONa » (4) Cl oul © oe, \=8 N=N OH S o CO JEE Advanced 2017 Solved Paper ‘The order of basicity among the following compounds is MN Ni OL nyc? Su, NON HNN A 1 m mm Vv (A) erervemt @ w>n>m>1 © Werte ©) betvenen ESsonen ‘This section contains 7 questions. Each question has 4 options. (A),(B), (C)and (D). ONE or MORE THAN ONE of these four ‘options is (are) correct. 8 ‘The correct statement(s) about surface properties is(are) (A) Adsorption is accompanied by decrease in enthalpy and decrease in entropy ofthe system (B) The critical temperatures of ethane and nitrogen are 563 K and 126 K, respectively. The adsorption of ‘thane will be more than that of nitrogen on same amount of activated charcoal ata given temperature (© Clouds an emulsion type of colloid in which liquid is dispersed phase and gas is dispersion medium (©) Brownian motion of colloidal particles docs not depend on the size ofthe particles but depends on viscosity of the solution 9, Forareaction taking place in a container in equilibrium with its surroundings, the effect of temperature on its equilibrium ‘constant K in terms of change in entropy is described by (A) With increase in temperature, the value of K for ‘exothermic reaction decreases because the entropy change of the system is positive (B) With increase in temperature, the value of K for ‘endothermic reaction increases because unfavourable ‘change in entropy of the surroundings decreases (© With increase in temperature, the value of K for ‘endothermic reaction increases because the entropy ‘change of the system is negative (©) With increase in temperature, the value of K for exothermic reaction decreases because favourable ‘change in entropy of the surroundings decreases 10, Inabimolecular reaction, the steric factor P was experimentally determined to be 4.5. The correct option(s) among the following is(are) (A). Theactivation energy of the reaction is unaffected by the value of the steric factor (B) Experimentally determined value of frequency factor is higher than that predicted by Arthenius equation (© Since P=4.5, the reaction will not proveed unless an effective catalyst is used (D) The value of frequency factor predicted by Arrhenius ‘equation is higher than that determined experimentally 1. For the following compounds, the correct statement(s) with respect to nucleophilic substitution reaction is(are) Co Cr o ay GP_3021CHEMISTRY 2 2B. 4. H, cH, oa I H,C—C— Br Br cH, ay vy (A) Landi fdlowS,1 mechanism (B) Landi follow$,2 mechanism (©) Compound IV undergoes inversion of configuration (0) Theorder of reactivity fo 1, I and 1V is: 1V>1> I Among the following, the correct statement(s)is(are) (A)_Al(CH,)s has the three-centre two-electron bonds in itsdimerie structure (@) BH; has the three-centre two-electron bonds in its dimeri structure (© AICI, has the three-centre two-electron bonds in its dimeric structure (©) TheLewis acidity of BC, i greater than that of AICI, ‘Tae option(s) with only amphoteric oxides isfare) (A) C1,0,,BeO, Sn0, S10, ®)_x,0,,C10, $n0, POO (© NO,B,0,,P60,n0, (©) 210, A1,0,,Pb0, PLO, ‘Compounds P and R upon ozonolysis produce Q and S, respectively. The molecular formula of Qand $ is CsH,0.Q undergoes Cannizzaro reaction but not halofoem reaction, ‘whereas $ undergoes haloform reaction but not Cannizzaro reaction @ P a wyZaiH20” (cyHx0) noyone, i) R @ RANeaBO? ceo, ‘The option(s) with suitable combination of P and R, respectively, is(are) (a) HC: © SEs This section contains 2 paragraphs, each describing theory, experiments, data ce. four questions related to the two paragraphs with two questions on each paragraph, Each question has only ‘one correct answer among the four given options (A), (B), (C) and (0). PARAGRAPH UponheatingKCIO, inthe presence ofeatalytic amount ofMnO,, agas Wis formed ExtessamountofW reacts with white phosphors to give X. The reaction ofX with pure HNO, gives Y and 18. Wand X ar, respectively (A) O,and P,0, © Oj and POjo 16. Yand Zar, respestively (A) N,OsandH1,PO, —@)_NOsand IPO, (© NjOyandHPo,’ — (D)_NjO, and H, PS, PARAGRAPH? ‘Thereaction ofcompound Pwith CH, MgB (excess) n(CyH),0 followed byaddition of H,OgivesQ Thecompound Qontreatment with H,SO, at 0°Cgives R. The reaction of with CHjCOCLin the (B) O, and P,O, o Otand PLOsy presenge anhydrous in CHC followedbytreatment with 1,0 produces compound $ [Et in compound P is ethyl group} Hoy oS Et —>Q—> R—+S 17, “The produ is aoe “w H,coc WoC HSC. cH, © | HOS coct, The reactions, Qto R and R to, are (A) Dehydration and Friedel-Crafts acylation (B) Aromatic sulfonation and Friedel-Crafts acylation Friedel-Crafts alkylation, dehydration and Friedel Crafts acylation (D)_Friedel-Crattsalkylation and Friede!—Craftsacylation2 JEE Advanced 2017 Solved Paper SOLUTIONS Paper - 1 ABO 3 (A) During adiabatic expansion, the final temperature is less than the initial temperature. ‘Therefore the final volume in adiabatic expansion will also be less than ‘the final volume in isothermal expansion, This can be graphically shown as fe VAT) reversible otbermal ‘everble aiatic ‘The magnitude of work done by the gas is equal tothe aa under thecurve. As een ffom the figure the area under curve in reversible isothermal is more, Hence, the magnitude of work done is lesser in adiabatic reversible expansion as compared to the corresponding, work in isothermal expansion. 4 (8) _Infecexpansion, P= 0. W fcarried out isothermally (AU=0)=>q=0(Adiabatic) ; From! law If carried out adiabatically (q = 0) => AU (Isothermal) ; From I law: oF vy Y rN v During irreversible compression, maximum work is ddone on the gas (corresponding to shaded area) When T,=T, => AU=nC,AT=0 In reversible adiabatic expansion, T, HCI+ HOC HCI0,+ 1,0 > C10; +10" ‘Acid Basel Basel acid | Since 1,0 is accepting 11° from HICIO, so H,0 is stronger base compared to CIO; (GD) ‘The colour of X, molecules of halogens is due to absorption of light inthe visible region. The energy acquired inthis manner excites the valence electron fiom the highest occupied molecular orbital (HOMO) tothe lowest unoccupied molecular orbital (LUMO), ice, transition from x" to" molecular orbital X, :018, 0418, 028, 0°28, 02p2, 1p? © 2p,2, © 60) [cott.o),]cl, Serra [CON] Ch, % 0 Pink Solution 1:3 destoite HCI (excess) (d°sp' hybridisation of central roo epee ‘metal atom as NH, isa strong - field ligand) @ 3AgCI G09 of AgCI) isa weak field ligand) one) ra X and Z in equilibrium at 0°C = then equilibrium is shifted towards X, making colour of solution pink. GP_3021(CHEMISTRY 6 (A.B) TUPAC name a cH, 1 1 2 2 a) |-chloro-4-methylbenzence @) ‘4-chilorotoluene 3 3 4 cH; al 7. (BD) (B) _Bromination proceeds through trans-addition in both the reactions. Mand Nare identical, hence, M and O and N and P are two set of diastereomers, @) Br cn, i iH H a a cu; H = 1 cn, : cH, dL — ck, ony, i i Br trane-2-Butene veer Bromonien ion NY H CH, cHy Br Br cHy H cH, on Mand Wares (rawr Dione) Br ony i ; cH, el ” ; =o a cu, | BeBe H; H on, on — « F u vs CH; “Near eed-Buene ce-samnom in NS H cH, cH, Br pr—-un Br ~ Ht pr e cn, cu, @) and are enantiomers ‘ne2, }Divemebuare10, @ 6 6 (6) H, Hef Density(@)= f= msi = TN, (d= density) For FCC, Z Givena=4» 10-%em bom (11079) xoxo (tao) xox —— 8610 6410 + M= No. of atoms = —— “x Ny, 19 oF atoms lar mass 256 x10 610% 8x6x16 ~ ValueofN=2 =2«108 The formula for conductances G = x <# sx107 u “io K=6% 10Sscm™ «x1000_ 6x10 x1000 M0005 vs pina Ur] =104=ca=000150 104 D001 An. 1o* Ag 00015 Mn 1075 em? mote! ieen6 Species Numberoflone pars ‘on central atom @ [Tebr,P 1 Gi) (Br, 2 ii) SNES 0 (iv) [XeF 3 ‘Tetal number oflone pairs= 1+2+0+3=6 (it, Cl,, Bey, Cy, Nas F3) is? ~ (Diamagnetic) Glsotls! (Paramagnetic) ols! ot1s?,o2s? _(Diamagnetic) Gls! o*1s%,02s%,6¢2s? (Diamagnetic) ols, 0°18, 028%, 028%, 2p = x2p) (Paramagnetc) ols? o* 1s, 023%, 0°28, n2p% = 203 (Diamagnetic) 2 6 B. © 14.) JEE Advanced 2017 Solved Paper 02s, 6*2s*, x2p, = x2p},02p2 (Diamagnetic) als?,o* ols, 0", 0287, 61282, x2p2 ,72p% = n2pi,n*2p2 = x*2ph (Paramagneti) ols?, o* Is?, 0282, 6*2s?, 62p2 ,x2p% = nap}. n*2p8 = 0293 (Diamagnetic) OAD Ton-aromatie Anti-aromatic Nomaromatie Antaromatic AOg Aromatic Aromatic Aromatic ‘Aromatic Aromatic 1s wave function for He' is given by (2) Vad) 2 «(gold ice, itis independent of cos 0 ‘The probability of findingan electron at zero distance from the nucleus is zero. The probability increases ‘gradually asthe distance increases, goes tomaximum and then begins to decrease. Fora given orbital with principal quantum number, n ‘and azimuthal quantum numbr,é ‘Number of radial nodes = (n- ¢—1) Vem GP_3021CHEMISTRY 9 BO 16. (a) m © 18. 0) Lo 2 @) Referans 13. Energy needed toexcite from n=2ton=4 8 nh AE, 61362? « se0V on dividing, Alkylbenzenes when treated with Br, at high temperature, in the presence of sunlight and absence of halogen carrier undergo halogenation in the side chain, Thus fs A Bry Le. - Tea Toe Beruylcionide Benwy cinive Ope Oe von Hom Oo ‘COOH Perkin condensation of benzaldehyde with (CH,CO),0/CH,COOK yields cis and trans form of cinnamic acid, (OCHsCOONs GHGCHO + (CHZCO),0 OTN Cr cH = cHCOOH Berzaldehyde Acetic anhydride (DH? inamic acid ‘dsand vane Paper - 2 {As Tincrease, VP. increases at Km 4.51000 46 %500 T-20K 273~ Zn(s)+ Cups > Znf’ + Culs) Yaa) Given (2n2"]= 10{Cu"} AG=-2F (1.1) +2303 RT logi910=2.303 RT-2.2F10 3 (A) Ate aG=0 @-)= = 14510 5 = 145 «10°Pa 1. asx «10°+ 1Pa 14500 105+ 1= 14501» 105Pa= 14501 Bar 4. (© Fe+conc. HNO, > Fe,0, Cu cone. HNO} -»CuNO, +NO, + H,0 4Au + 8NaCN +0, + 21,0 ->4NafAu(CN))+4NSOH Zn+ NaOH» NaZn0,+ Hy (©) Correct order HPO, > H,P,0g > HyPO3 > HPO, by ebay Gy © Step: ONINOR HOLE, aH Mu, Naw & Step2: vas) Diazocoupling ire He 2O fy #4 ua vn sia, Sint avy The conjugate acid is stabilized by resonance with two different “NH group. Hence electron density increases on N of = NH ve We Cy on Sw cs Sin, o JEE Advanced 2017 Solved Paper The conjugate acid is stabilized by resonance with ‘one -NH, group. Hence as compared to IV lesser increase of electron density on N of = NH NANT Hog 0) Lone pair is not involvd in aromaticity. Hence more available ) ay Lone pair is involved in aromatic sextet, Hence not available Hence the corteet order of basic strength is Iv> I> > (A,B) (A) As adsorption is spontaneous, AG for the process is ve. Adsorption is accompained by decrease in randomness, Therefore AS and TAS for the process is also negative. As AS for the process is —ve and the ‘process is spontaneous, AH for the process has to be “ve ie, enthalpy of the system decreases. Under a given set of conditions of temperature and pressure the easily liquefiable gases e.g. C,H, NH, ‘and HCI are adsorbed more than the gases like N, H, and CO. The ease with which a gas-can be liquefied is determined by its critical temperature. Critical temperature is the minimum temperature above ‘which a gas can be liquified. This implies that gases ‘with high critical temperature values can be easily liquified as compared to gases with low critical temperature value. (A,B,D) (A,B) The Arrhenius equation is k= AetaRt ‘where A= Pre-exponential factor Aiisnot directly related with temperature and activation energy. NH Where A= Zk P (Frequency factor)” (tei factor) Hence we can say the Ei independent of strc factor p- Kaul K theoretical $0, Axoat ” Aired GP_3021CHEMISTRY un 1. ABO, c I 0 (Cmte ef Broan rates é Land I follow S,2 als, as both ae 1° halide (© Compound (IV) undergoes inversion of configuration due to presence of chiral carbon atom. 12. (A,B,D) (A) Structure of AL(CH,), 3C-2e" Bond B) Structure of BH, 1 GX B LS 3c-26° iC (© SteuctureofAL,Cl, ON el ae Na “er (©) BCI, is stronger lewis acid as the bond formed with the base will involve 2p orbital overlap which isstronger than 3p orbital overlap in the case of AICI, 13, (A.D) NO=>Neutral BO, = Acidic CO= Basie Allothe oxides are amphoteric 14. (A,B) an) Y Woveitsls a l © ay A BOERS > Q(CiHLO) i, CH nen () « a \(+ve cannizaro reaction) ° 1 c ° 00,0140, Neu i WzZnto > 3 +H-CH ne (© (+e haloform reaction)R 18, n. JEE Advanced 2017 Solved Paper ant a +cH, le Mis (-ve cannizaro reaction) @) @ 2 9 »N \ i Oo cH oven, CY it, +H, -E-cH, ta Nau, cH, (Gve haloform reaction) ) © © & 6B) KCIO,; 3 KCI+ 0 ° om P+ 0; P00 (bie) (exces) Ox) P,O,,+HNO,—> Nz05+HPOS w wo & 8 © 9 OMe CCH), 6 j “OF cI OL) P) ” [x0 HoH 0" O-H CCH), CH): cCHy, ~cH,-¢-cH, OU OL [0 (Getyaraon) @ cH, ® ci, -C-c1/alcl, ‘Geylation) cH, CCH) CH Coch, o GP_3021(CHEMISTRY ‘Which of the following compounds will form significant amount of meta product during mono-nitration reaction ? ‘OH OCcOCH, a a The increasing order ofthe reactivity ofthe following halides for the Sy! reaction is CHLCHCH CH, CHCHCH,CL a a 0 PrH,CO-C,H,-CH,CL a @ ay Na,Zn0, (B) 2n0+C0,-+ZnC0, (1) base and acid 2) base and base @) avid and acid @) avid and base Both lithium and magnesium display several similar properties due to the diagonal relationship; however, the ‘one which is incorrect is (1). Both form basic carbonates, (2) Both form soluble bicarbonates (@)_ Both form nitrides Nitrates ofboth Liand Mg yield NO, and O; on heating 3-Methyl-pent-2-ene on reaction with HBr in presence of peroxide forms an addition product, The number of possible stereoisomers for the product is () S% @) Zer0 @) Two Four ‘A metal erystallises in a face centred cubic structure. Ifthe ‘edge length ofits unit cell is’, the closest approach between two atoms in metallic erystal will be () @ Wa @) Va @ ¥ ‘Two reactions R, and R, have identical pre-exponential factors. Activation energy of R, exceeds that of Ry by 10k mot". Ifk; and k, are rate constants for reactions Ry and respectively at 300K, then In(ky/k,) is equal to (R=8314J mol !K"}) m8 @r @ 6 wam2 4 16. 17. The correct sequence of reagents for the following ‘conversion will be HQ CH, : “0 CHO cH,” (1). TAg¢NHL),]” OFF, HY/CH,OH, CH; MgBr @)_CHjMgBr, H*/CH,OH, [Ag(NH,),]* OF" G)_CHjMgBr, [Ag(NH),)° OFF, H'/CH,OH (4) [Ag(NHL),]* OF, CH,MgBr, H'/CH,OH ‘The Tyndall effect is observed only when following, ‘conditions are satisfied (@) The diameter ofthe dispersed particles is much smaller than the wavelength ofthe light used (b) ‘The diameter of the dispersed particle is not much smaller than the wavelength ofthe light used. (©). The reftactive indices of the dispersed phase and dispersion medium are almost similar in magnitude (@) The refractive indices of the dispersed phase and dispersion medium differ greatly in magnitude. (1) (@and(@) @) (banda) G) (@and(o) (4) (byand(e) ‘Which ofthe following compounds will behave asa reducing, sugar in an aqueous KOH solution? HOH 9. CHOW 1 i HYScoc, HOILC So. cHhoHt HOH. o. CHLOH ‘ Pi Hy none Q.CH,OCH, ) Kou on ou Given Cigraphie) * O18) > COLE) + AJP =-393.5 ki mot! 1 Hy (g)+ 50,8) > H,00); a 19. 20, 24. 2. 24 JEE MAIN 2017 Solved Paper CO4(g)+ 2H,O() + CHY(g)+ 20,62). AHP =+8903kJmot"! ‘Based on the above thermochemical equations the value of| A HP at 298 K forthe reaction C eahite)* 2H(8) —> CH,(g) will be () +748kImort ——Q) +1440 mot! @) =748kImor 4) = 144.0kF molt ‘Which of the following reactions isan example of a redox reaction? ())_ Xe, +0,F, > XeF, +0, Q)Xck, + PFs > [XeF]* PF @)_ XcFg+H,0-> XcOF,+2HF () Xek,+2H,0—> Xe0,F,+4HF ‘The products obtained when chlorine gas reacts with cold and dilute aqueous NaOHare (@) ClO-andclos ——@)_Clogand clog @) Cr-andcio- @ Crand clos “The major product obtained inthe following reaction is Be CH, _‘BuoK, cng 0) yCGHGCHKOBUICHACHs Q) CH CH= CHC,H, 8) CC HCHOBICH,CoH, 4) COCHGCHLO'BUICHCHH, Sodium salt of an organi acid" produces effervescence with cone, H,SO,,'X'reats wit the acidified aqueous CaCl, solution to give whit prespitate which declourises acidic solution of KMnO, (1) CglgCOONa @) HCOONa @) CHjCOONa @) NaxC0, Which of the following species is not paramagnetic ? @ NO @ @) 0, ® B ‘The freezing point of benzene decreases by 0.45°C when 0.2g of acetic acid is added 1020 g of benzene. ITacetic acid associates to form a dimer in benzene, percentage association of acetic acid in benzene willbe (K for benzene= 5.12 kg mol!) () 646% @ 804% 0) 16% ) 146% Which of the following molecules is least resonance stabilized? 0 O oll J GP_3021(CHEMISTRY ZF @ I ® SN 0’ 25. On treatment of 100 mL of 0.1 Msolution of CoC. 6H,0 with excess AgNOs; 1.2 = 102? ions are precipitated. The complexis: (@) [Co(H,O),C1,]C12H,0 2) [ColH,0);C1,]3H,0 B) [ColtH,OVJIC1; (4) [Co(H,0),C1}C1,H,0 26, The major product obtained in the folowing reaction is 7 DIBAL-H. ‘coor on on 0 THO @ qo ‘coon ‘cHo 8 rer ® Qe ‘coon clo 2. 28, 29, 30, mins ‘A water sample has ppm level concentration of following 0,803-= 100, NOs =50 the anion/anions that make/makes the water sample Unsuitable for drinking isare () only NOS both $0}- and NOs B) only @) only SOF 1 gram ofa carbonate (MjCO;) on teatment with excess HCI produces 0.01186 mole af CO,, The molar mass of M,CO, in gmol”" is () 1186 @ a3 @) 1186 @ 1186 Given . 36V.E8 5, = -O74V, eer eter Ee =1.33V,E° =LSIV. eyo 10 soz Among the followin, the strongest reducing agents Oa @Q) Mn+ @ co @ ‘The group having isoelectronic species is () OFF Nat, Mg @) O-.F.Na,Mg* (@) 0%. F,Na, Mg (8) OF LNat, Mg?aad JEE MAIN 2017 Solved Paper SOLUTIONS (@)_ Nitration takes place in presence of concentrated HINO, + concentrated H,S0, In strongly acidie nitration medium, the amine is converted into annum ion NH"), substitution is thus controlled not by ~ NH group but by ~ NIT;* ‘group which, because of its positive charge, directs the entering group to the meta-position instead of ortho, and para ° NH, Nitj gp: mairecting = Ni yp. 0, pirecting 3) From 1" lawofthermodynamies AU=q+w For adiabatic process qz0 AuU=w @) Since Sy1 reactions involve the formation of carbocation as intermediate in the rate determining, step, more isthe stability f carbocation higher will be the reactivity ofalkyl halides towards Sy! route ‘Since stability of carbocation follows order cH,-cr- Ct; on 190, Sie? 2n00; ° tee ied lt 10, (1) Mgcan form basic carbonate like 4 Henson, 3MgCOs. Mg(OH),. 31,01 aes regs While Li can form only carbonate (LiCO;) not basic uo foun carbonate. wicnon IL. (4) Iftwo chirality centres are created as a result of an (comsibcation) addition reaction four stereoisomers can be obtained ° as products cuy cH, ra = nZ Negi,” s ‘cis-3, methyl pent-2-ene 07 Soc, een [evs toi —CH-CH-CH,—CH, cH 2, Brome, meth pentane Eaters) cH, CH ht Br Be Hl HE-G- Cth on h cH, HC 1 on @ 16. (1) CH, CH, “ ee HOCH, 9 c1,0H noct, cr 0 —Agxou Wt Scatwcon Br H 4 Br OW ou OF Hemiketal H CH, HAC: H [pi ornine Gis Gls HOW OH cron aun a) evesiver | rats OF 12, (4) ForaFCC unitcell test _ ou va (a Reducing sugar) a-hydroxy ketone " f Raa closest distance (2) = 28. 8 QoSm6 n. 19, 20. 2. 2. 8) Given COja)+ 21,00 > CH) +20,(8), 4? =8903.(0) Cape) + 2 @)-> COB); ar L Hy(e)+ 70,8) > 1,010), AJP =-285 8k mot! i) A,H? = D(A Hous ~ (ArH? peatats 393.5kImot (i) 890.3 =[1(ay HP)cu, +2*0)]-L1(-393.5)+2(-285.9)] (6; Hau, = 8903-965. =74.8KI/mol (1) Inthe reaction sn Ker, +O,F, > Ker, +0, ia (8). Cly+ NaOH» NaCl+ NaCIO+H,0 [oold and dilute] (2) Elimination reaction is highly favoured if (@) Bulkier base is used (©) Higher temperature is used Hence in given reaction biomolecular elimination reaction provides majr product. cn is ‘ Calls cf SS 001+ Br (8) NagC,0, +150, > Na,S0, +COT +CO,1+1,0 (exe) NNagC0, +CaCly->CaC,Ogb + 2NaC1 . (oti) SCaC;0,1-42KMn0, +8150, tout K,$0, +5CaS0, +2MnS0, + 10CO, +8H,0 (cts) 2 1 NO->one unpaired electrons presentin * molecular oxbithence paramagnetic 2. 2 25. 26. @ 4 “ @ JEE MAIN 2017 Solved Paper €0-» of, 01.003. Ry 222 ‘no unpaired electron hence diamagnetic. ‘vo unaired electron hence paramagnet. 'B, contains two unpaired electrons hence paramagnetic Inbenzene 2CH,COOH = (CH,COOH), Ia aw - 1000 AT,= Kym @ 1-$=0527 a=0945 °% degree of association = 94.6% ° js nonaromatic and hence least reasonance stabilized whereas other three are aromatic. Molarity x Volume( ml) ‘Moles of complex = 1000 000. 1000 01 mole ‘Moles of ions precipitated with excess of 12x10 02x10 AgNO, 0.01 xn=002 -2 ttmeans 2CI- fons present in ionization sphere + complex is{Co(H,0),C1}CI, HO 2 moles DIBAL-Hisan clectrophilic reducing agent. Itreduoes both ester and carboxylic group into an aldehyde at GP_3021(CHEMISTRY mie low temperature, BW Foggy? ESV a p EB =136V onicr a Pogoitices =133V co,H CHO . am 27. (3) Above 2 ppm concentration of F- in drinking water etree cause brown mottling of teth Since Cr is having least reducing potential, so Cr is. 28 (2). Given chemical oq? the best reducing agent. M,CO,+2HC > 2MCI+H,0+CO, 30. (I)_Isoelectronie species have same no. of electrons. lem 001186 mot ions 2 Nag? fiom the balanced chemical eq $20 2 nM,CO;=n00, Noofe= 10 10 0 1 therefore OF, Nat, Mg*? are isoeletronie 1 = 001186 M,CO, 1 = M,CO, oori86 => M=843 gmimolCHAPTER Some Basic Concepts of Chemistry | cee JEE dvanced/ IIT- a 5’ Rms 1. Themodem atomic mass unit is based on (1980) 2. The total number of electrons present in 18 ml of water is (1980) 3. 3g ofasalt of molecular weight 30 is dissolved in 250 g of water. The molality of the solution is. (1983 - 1 Mark) The weight of 1 « 10%? molecules of CuSO, SH,Ois (2991-1 Mark) $8. The compound YBa,Cu,O,, which shows super- conductivity, has copper in oxidation state assume thatthe rare carth clement ytrium isin its usual +3 oxidation sate (1994-1 Mark) C Trae eontauecos 1. 27g of Al will react completely with how many grams of oxygen? (1978) @ 88 ) 16g © Re @ 242 2. A-compound was found to contain nitrogen and oxygen in the ratio 28 gm and 80 gm respectively. The formula of compound is (1978) @ NO () N,0, © N,, @ NO, 3. The largestnumber of molecules isin (1979) (@) 36gofwater (b) 28 gofcarbon monoxide (©) 46 g ofethyl alcohol (@) 54 gofnitrogen pentoxide 4. The total number of electrons in one molecule of carbon dioxide is (1979) @ 2 ) 4 ©) 6 @ 8 A gaseous mixture contains oxygen and nitrogen in the ratio of | 4 by weight. Therefore the ratio of their number of molecules is (1979) @ ba © 18 © 7:32 @ 3:16 2. 1B. MW 2.16 g ofsilver carbonate on being strongly heated yields a residue weighing (1979) (@) 216g (b) 2488 (© 232g (@) 2648 Mis molecular weight of KMn0,, The equivalent weight of KMnO, when itis converted into K,MnO, is (1980) @ M () M3 (© Mis @ M7 1£0,50 mole of BaCl, is mixed with 0.20 mol of Na,PO,, the ‘maximum number of moles of Ba,(PO,), that canbe formed is (1981-1 Mark) (@ 070 (®) 050 (©) 020 (@ 010 One mole fN;H, loses ten mols of electrons to form anew compound Y. Assuming that al the nitrogen appears inthe new compound, what isthe oxidation sat of nitrogen in ¥? (There is no change inthe oxidation stat of hydrogen). (1981-1 Mark) @ 4 © 3 @ 8 (@ + The oxidation numberof carbon in CHO is © (1982-1 Mark) @ -2 () +2 @ 0 (@) +4 Armolal solution isone that contains one mole ofa solute in (1986-1 Mark) @ ® 1000 g ofthe solvent one litre ofthe solvent (©) one litre ofthe solution () 224liteesofthe solution The brown ring complex compound is formulated as {[Fett1,0),(NO))SO,, The oxidation state of iron is @ 1 () 2 (1987-1 Marky @3 @o The equivalent weight of MnSO, is half ofits molecular ‘weight when itis converted to (1988-1 Mark) @ Mn,0, (&) MnO, ( Mnoy (@ Moo} In which mode of expression, the concentration ofa solution remains independent oftemperature? (1988 Mark) (@) Molarity (6) Normality (©) Formalty (d) Molality GP_302115, 16. v. 20. a. 2. 2B. m4, opie. wise Sotved Papers - CHEMISTRY ‘The oxidation number of phosphorus in Ba(H,PO,)> is: (1990-1 Mark) @ 8 ) 2 on @ = The oxidation states ofthe most electronegative element in the products ofthe reaction, BaO, with dil. H,SO, is (1991-1 Marky (b) -Land—2 (@ —2and-1 (1992 - 1 Marky (a) Oand-1 (©) -2and0 Forte redx easton MaO} + CO} +H» Mn8*+ C0, +140 the core coecents ofthe reactants forthe balanced reaction are (1992-1 Mark) Mn0z Cx a @ 2 5 6 ® 6 5 2 @ 5s 6 2 ® 2 6 s The normality of 0.3 M phosphorous acid (H,PO; is, (1999-2 Marks) @ a () 09 © 03 @ 06 The oxidation number of sulphur in Sy, SF, HS respectively, are (1999-2 Marks) @ 0,+1and-2 () #2,41and-2 (©) 0,+1and+2 (@ -2+1and-2 Amongst the following identify the species with an atom in +6 oxidation state (20008) ©) Mn0x (6) CHONE (© Ni @ C0,Cl, ‘The reaction, 3C1O-(aq) —» C10 ; (aq) + 2C1aq), isan exampleof 20015) (@)_ oxidation reaction (©) reduction reaction (©) disproportionation reaction (@)_ decomposition reaction ‘An aqueous solution of 6.3 g oxalic acid dihydrate is made up to 250 mi. The volume of 0.1 N NaOH required to completely neutralize 10 mil ofthis olution is (20018) @ Om () 20m (© 10m (4m In the standardization of Na,S,0, using K,Cr,0, by ‘odometry, the equivalent weight OfK,Cr,0,i8 (20018) (@) (molecular weighty2 (©) (molecular weighty’6 (©) (molecular weighty3 (6) same.as molecular weight Howmany moles of electron weigh one kilogram? (2002S) L 108 x10 (2) 6.02310 © 6023 sos © 5508"! recor 2S. Which has maximum number of atoms? (20038) (@) 24gofC(12) (b) SogofFe(56) (©) 27gofAl(27) (d) 108g of Ag (108) Mixture X= 0.02 mol of [Co(NH,),S0, Brand 0.02 molof [Co(NH,),Br]SO, was prepared in tre ofsolution. 20035) | ite ofmixture-X++ excess AgNO, —_ ¥. {ite of mixture X+ excess BaCl, —_, Z ‘No. ofmoles of Y and Zare (@) 001,001 (b) 0.02,001 (©) 001,002 (d)_0.02,002 27. The pair ofthe compounds in which both the metals are in the highest possible oxidation state is (20048) ©) [Fe(CN)g]*[CO(CN) 6} (db) CrO,C1,,Mn0g (©) Tis,MnO, (d) [Co(CN),}".MnO, 28, Consider a titration of potassium dichromate solution with acidified Mohr's salt solution using diphenylamine as indicator. The number of moles of Mohs salt required per mole of dichromate is, (2007) @ 3 ) 4 5 @ 6 E Bie 1. What weight of AgCI willbe precipitated when a solution containing 4.77 g of NaCl is added ta solution of 5.77 got AgNO,? (1978) 2 One gram ofan alloy of aluminium and magnesium when tweated with excess of dil, HCL forms magnesium chloride, aluminium chloride and hydrogen. The evelved hydrogen, collected over mercury at 0°C has a volume of 120 litres at 0.92 atm. pressure. Calculate the composition ofthe alloy. (H=1,Me=24,a1=27) (1978) 3. Igniting MnO, converts it quantitatively to Mn,0, A sample of pyrolusite is ofthe following composition | MnO, 80%, SiO, and other inert constituents 15%, rest being water, The ‘sample is ignited in air to constant weight. What is the percentage of Mn in the ignited sample? (1978) [0=16,Mn=349] 4.4215 g ofa metalic carbonate was heated ina hard glass tube and the CO, evolved was found to measure 1336 ml at 27°C and 700 mm pressure. What is the equivalent weight of the metal? (1979) @) 55 gofamintureof FeSO, 7H,0 and Fe,(S0,),. 9,0 requires 4 ml of0.1 NKMn0, solution for complete exidation. Calculate the number of gram mole of hydrated ferric sulphate inthe mixtureSome Basic Concepts of Chemistry § ——________ 4 10. (b) The vapour density (hydrogen = 1) of a mixture consisting of NO, and N,O, is 383 at 26 7°C. Calculate ‘the number ofmoles of NO, in 100g ofthe mixture 979) 5 mil ofa gas containing only carbon and hydrogen were ‘mixed with an excess of oxygen (30 ml) and the mixture exploded by means ofan electri spark. After the explosion, the volume of the mixed gases remaining was 25 ml, On adding concentrated solution of potassium hydroxide, the volume further diminished to 15 mi ofthe residual gas being pure oxygen. All volumes have been reduced to N.T.P Calculate the molecular formula ofthe hydrocarbon gas. zz) In the analysis of 0.500 g sample of feldspar, a mixture of chlorides of sodium and potassium is obtained which ‘weighs 0.1 180g. Subsequent treatment of mixed chlorides with silver nitrate gives 0.245 1g ofsilver chloride. What is the percentage of sodium oxide and potassium oxide in feldspar. (1979) ‘A compound contains 28 percent of nitrogen and 72 percent cof metal by weight. 3 atoms of metal combine with 2 atoms OfN. Find the atomic weight ofmetal (198) ()_Asample of MnO, 44,0 is strongly heated in ai. The residue is MnO, (i) The residue is dissolved in 100 ml of 0.1 N FeSO, containing dilute H,S0, (ii) ‘The solution reacts completely with 50 ml of KMnO, solution (iv) 25mlofthe KMnO, solution used in stp (ii) requires 30m of. N FeSO, solution for complete reaction Find the amount of MnSO, 4H,0 present inthe sample. (1980) (@) One litte ofa sample of hard water contains 1 mg of CaCI, and 1 mg of MgC. Find te total hardness in terms of parts of CaCO, per 10® parts of water by weight. (6) Asample ofhard water contains 20 mg ofCa"* ions per litre. How many milli-equivalent of Na,CO, would be required to soften I litre ofthe sample? (©) 1.gmof Mg is burnt in a closed vessel which contains 0SgmofO, © Which reactant islet in excess? (Gi) Find the weight of the excess reactants? Gi), Howmay milliliters of0.5'N H,SO, will dissolve the residue in the vessel (1980) A hydrocarbon contains 10.5g of carbon per gram of hydrogen. | litre ofthe vapour of the hydrocarbon at 127°C and | atmosphere pressure weighs 2.8g, Find the molecular formula 19s) 2. 13. 1 18. 16. W. Find (i) The total number of neutrons and (id) The total mass ofneutron in 7 mg of ¥C. (Assume that mass of neutron = mass of hydrogen stom) A mixture contains NaCl and unknown chloride MCI. () 1 g ofthis is dissolved in water. Excess of acidified ‘AgNO, solution is added to it 2.567 g of white ppt. is formed (1 goferiginal mixture isheated to 300°C. Some vapours ‘come out which are absorbed in acidified AgNO, solution, 1.341 gof white precipitate was obtained. Find the molecular weightof unknown chloride. (1980) ‘A 1,00 am sample of H,O, solution containing X'per cent H,0, by weight requires ml of a KMnO, solution for complete oxidation under acidic conditions. Calculate the normality ofthe KMnO, solution. (1981 - 3 Marks) Balance the following equations. (1980) (@ QKO+HT+ NOs > Cu" +NO+H,O (1981-1 Marky (i) K,[FACN),J+H,80,+H,0 > K,80, + FeSO, +(NH,),80,+CO (1981-1 Mark) (ii) C,H,OH+ 1,4 OH > CHL, + HCO 5 +1 +H,0 (1981-1 Mark) Hycroxylamine reduces iron (Il) according to the equation: 2NHLOH +4 Fe > N,O(g) T+ H,0 +4 Fe® +41 Iron (II) thus produced is estimated by titration with standard permanganate solution. The reaction is MnO; +S Fe2*+ 8H" ‘A.10 ml sample ofhydroxylamine solution was diluted to 1 litre. 50 ml. of this ciluted solution was boiled with an excess ofiron (ID solution. The resulting solution required 12m of 0.02 M KMnO, solution for complete oxidation of iron (UD). Calculate the weight of hydroxylamine in one litre ofthe original solution. (H= 1, N= 14, = 16, K=39, Mn=S5, 6) (1982-4 Marks) The density of a 3 M sodium thiosulphate solution (Na,S,0,) is 1.25 g per ml. Calculate (i) the percentage by weight of sodium thiosulphate, (i) the mole faction of sodium thiosulphate and (i) the molaities ofa’ and S,0,2- ions (1983 -§ Marks) 408 gofamixture of BaO and an unknown carbonate MCO, ‘was heated strongly. The residue weighed 3.64 g. This was dissolved in 100 ml of !N HCL The excess acid required 16 ml of 25 N NaOH solution for complete neutralization [dentify the metal M. (1983-4 Marks) (At wt H=1, C= 12,0=16,C1=355,Ba= 138) Mn2* +5 Fe! +4H,0opie. wise Sotved Papers - CHEMISTRY 19, 20. a 2. 2B. 24, 25, Complete and balance the following reactions: (Zn NOs 9204 NH} (1983-1 Mark) (i) Cr,03" +C4Hj0-> CHO, +C* (1985-1 Mark) (ii) HNO, +HCI>NO+Cl, (1983-1 Mark) (iv) Ce + 8,03" SOP +Ce* () Ctl Cr+ C10- (4983 - 1 Mark) (1983 - 1 Marky (vi) Mn+ PbO,>MnOg +H,O (1986-1 Mark) (vi) S+ OH S?-+ 8,03 (1986-1 Mark) (il) CIOs +1-+H,S0,-> C+ HSO% (1986-1 Mark) () AgtAsH> HAsO, +H (1986-1 Mark) 2.68» 10° molesofa solution containing an ion 4" requite 1.61 « 10° moles of MnO for the oxidation of 4"* to 'AO} in acid medium, What isthe value of n? (1984-2 Marks) Five of 8Nniticaci, 48 ml of SN hydrochloric acid and a certain volume of 17M sulphuric acid are mixed together and made upto 2itee. Thirty ml ofthis acid mixture exactly neutralise 42,9 ml of sodium carbonate solution containing ene gram ofNa,CO,,10H,0 in 100m of water. Calculate the amount in gram ofthe sulphate ions in solution (1985 - 4 Marks) Arrange the following in inereasing oxidation number of iodine, (1986-1 Mark) 1,,HI,HIO,,ICl (What isthe weight ofsodium bromate and molarity of solution necessary to prepare 85.5 ml of0 672 N solution ‘when the halfcell reaction is BiO3 +611" + 66> Br-+3H,0 i) What would be the weight as well as molarity ifthe half-cell reaction is: 2BrO; + 12H*+ 10e-—> Br, +6H,0 (1987-5 Marks) A sugar syrup of weight 214.2 g contains 34.2 g of sugar (C jlagO,).Caleulate: (i) moll concentration and i) moe fraction of sugar in the syrup. (1988-2 Marks) A sample of hydrazine sulphate (N;H,SO,) was dissolved in 100 mi of water, 10 ml of this solution was reacted with excess of ferric chloride solution and warmed to complete the reaction, Ferrous ion formed was estimated and it required 20 ml, of M/SO potassium permanganate solution, Estimate the amount ofhydrazine sulphate in one litre ofthe solution (1988-3 Marks) 6. n. 28, 29, 3. 32. Reaction SF +N,H, Ny + 4F +H MnOj + SFe?* + 811" > Mn?" + SFe?* + 41,0. ‘An equal volume ofa reducing agent is titrated separately with IM KMn0, in acid neutral and alkaline media. The volumes ofKMrO, required are20 min acid, 334ml. neutral and 100 ml inalkaline media. Find outthe oxidation state of| manganese in each reduction product. Give the balanced equations forall the thre half reactions. Find out the volume of IM K,Cr,0, consumed; if the same volume of the reducing agent ititrated in acid medium. (1989 -$ Marks) Armixture of H,C,0, (oxalic acid) and NaHC,O, weighing 2.02 was dissolved in water and solution made upto one litre. Ten miliites ofthe solution required 3.0m, of 0.1N sodium hydroxide solution for complete neutralization, In another experiment, 10.0 ml, ofthe same solution, in hot dilute sulphuric acid medium. requite 4.0 mi. of 0.1 N Potassium permanganate solution for complete reaction Calculate the amount of H,C,O, and NaHCO, in the mixture (190° 5 Marks) solid mixture (50 consisting oflead nitrate and sodium nitrate was heated below600°C until the weight of thersidue ‘was constant. Ifthe loss in weight is 280 percent, find the amount oflead nitrate and sodium nitrate inthe mixture. (1990-4 Marks) Calculate the molality of 1 litre solution of 93% H,SO, (weight/volume). The density ofthe solution is 1.84 g/ml. (1990-1 Marks) {A solution of 0.2 of a compound containing Cu2* and 207 ons on titan with 02 MKMn0,in presence of 80, consumes 226 ml of the oxidant ‘The resultant scluionsneutlized with NajCO. aed ith sete dcidandteaed with exces Kt Th liberated iodine rqutes TI 3mlof0.05 MNa,S,0, sluten fr eomplteredtion Find out the molar ratioof Cu?* to C02" in the compound Write down the balanced redox reactions involved in the above titrations, (1991 - 5 Marks) A.1.0 gsample of Fe,O, solid of 55.2% purity is dissolved in acid and reduced by heating the solution with zine dust. ‘The resultant solution is cooled and made upto 100.0 ml. An aliquot of25.0 ml of this solution requires 17.0 ml of 0.0167 ‘Molution of an oxidant for titration. Calculate the number of electrons taken up by the oxidant in the reaction of the above titration. (1991-4 Marks) 42.0 g sample of a mixture containing sodium carbonate, sodium bicarbonate and sodium sulphate is gently heated till the evolution of CO, ceases. The volume of CO, at 750 ‘mm Hg pressure and at 298 K is measured to be 123.9 ml. A 1 Sg ofthe same sample requires 150 ml, of (M/10) HCL for complete neutralisation. Calculate the % composition of the ‘components of the mixture. (1992 - § Marks)Some Basic Concepts of Chemistry § ——________ 4 33. One gram of commercial ANO, is dissolved in 50 ml, of water Its treated with 50 ml, of a KI solution, The silver ‘odide thus precipitated is filtered off Excess of KI in the filterateis titrated with (M/10) KIO, solution in presence of 6MHCItil all Fons are converted into ICI. Itrequires SO ml cof(M/10) KIO, solution, 20 ml. ofthe same stock solution of| KI requires 30 ml. of (M/10)KIO, under similar conditions Calculate the percentage of AgNO, inthe sample (Reaction : KIO, +2KI-+6HC1—> 3ICI+ 3KC1+ 34,0) (1992-4 Marks) 34, Upon mixing 45.0 ml. of0.25 M lead nitrate solution with 25.0 ml of, 10 M chromic sulphate solution, precipitation of| lead sulphate takes place. Howmany moles oflead sulphate are formed” Also, calculate the molar concentrations of the species left behind inthe final solution, Assume that lead sulphate is completely insoluble (1993 - 3 Marks) 35, The composition ofa sample of Wustit is F530} 00 ‘What percentage of te iron is present in the form of Fe ay? (1994 - 2 Marks) 36. 8.0575 « 10 kg of Glauber’s salt is dissolved in water to ‘obtain | dm? of solution ofdensity 1077.2 kg m>. Calculate the molarity, molality and mole faction of Na,SO, in the solution (1994-3 Marks) 37. A300gsample containing Fe,0,,Fe,0, andan inertimpure substance, is treated with excess of KI solution in presence ofdiluteH,SO, The entre iron is converted into Fe along with the liberation ofiodne. The resulting solutions diluted 0 100ml A20:mlof the diluted solution requires 11,0 ml of 0.5 MINa,S,0, solution to reduce the iodine present. ASO ri ofthe diluted solution, ater complete extraction ofthe ‘odie requites 12,80 ml of0.25 MKMnO, solution in dilute H,S0, medium for the oxidation of Fe. Calculate the percentages of Fe,O, and Fe,0, inthe original sample. (1996-5 Marks) 38, An aqueous solution containing 0.10 gKIO, formula weight = 214.0) was treated with an excess of KI solution, The solution was acidified with HCI, The liberated I, consumed 45.0 mL of thiosulphate solution to decolourise the blue starch-iodine complex. Calculate the molarity ofthe sodium thiosulphate solution, (1998-5 Marks) 39, Howmany millilitres of0.5 MH,SO, are needed to dissolve 0.5 gofcopper(tt) carbonate? (1999-3 Marks) 40, A plant virus is found to consist of uniform eylindrcal particle of 150 Ain diameter and $000 A long. The specie volume of the virus is 0.75 em'/g, Ifthe virus is considered to bea single particle, find its molar mass (1999-3 Marks) 411. Hydrogen peroxide solution (20 ml) reacts quantitatively witha solution of KMnO, (20 mi) acidified wit dilute H,S0, Thesame volume ofthe KMn0, solution is just decolourised by 10 ml of MnSO, in neutral medium simultaneously forming a dark brown precipitate of hydrated MnO,, The brown precipitate is dissolved in 10 ml of 0.2 M sodium oxalate under boiling condition in the presence of dilute H,S0,. Write the balanced equations involved in the reactions and calculate the molarity of H,0,, (2001 - 5 Marks) 42, Calculate the molarity of watrifits density is 1000 kg/m* (2003-2 Marks) 5 ESS 1. Read the following statement and explanation and answer as per the options given below STATEMENTS): Inthe titration ofNa,CO, with HClusing methyl orange indicator, the volume required at the equivalence point is twice that ofthe acid required using pphenolphthalein indicator. EXPLANATION€E) : Two moles of HCl are required for the complete neutralization of one mole of Na,CO, (1991 - 2 Marks) (@) Both and E aretrue, and E isthe correct explanation ofS. (6) BothS and Earetruc, but Eis not the correct explanation ofS. (©) Sistruebut E is false. (@ Sisfalse but Eis true. 1 Eee 1. A student performs a titration with different burettes and finds titre values of 25.2 mL, 25.25 mL and 25.0 mL. The ‘numberof significant figures in the average titre value is 2010) 2 Silver atomic weight = 108 g mo") hasa density of 10.5 8 em’. The number of silver atoms on a surface of area 10")? 1m? can be expressed in scientific notation as y « 10%. The value of x is 2010) 3. Thedifference in the oxidation numbers ofthe two types of sulphur atoms in Na,S,04 is (2011) 4. Ifthe value of Avogadro number is 6.023 « 1023 mol-! and the value of Boltzmann constant is 1.380 * 10°23 )K-!, then the number of significant digit in the calculated value of the universal. gas constant is (JEE Adv. 2019)oy 1 opie. wise Sotved Papers - CHEMISTRY I Secton-s Ina.compound C, Hand N atomsare present in 9: 1: 3.5 by ‘weight, Molecular weight of compound is 108, Molecular formula of compound is [2002] (CN, (0) GHN (©) CAN, @CyH,NS. With increase of temperature, which ofthese changes? 12002) (@)_ molality (b) weight fraction of solute (©) molarity (@) mote fraction, Number of atoms in 558.5 gram Fe (at. wt. of Fe= 55.85 smol")is (@) twice that in 60 g carbon (b) 6023 x 10% (©) halfthat in 8 g He (@) 5585 x 6.023 x 108 ‘What volume of hydrogen gas, at273 Kand | atm. pressure will be consumed in obtaining 21.6 g of elemental boron (atomic mass= 10.8) from the reduction of boron trichloride by hydrogen ? 12003] @ 612L () 48L © BAL @) 896L 25m| ofa solution of barium hydroxide on titration with 20.1 ‘molar solution of hydrochloric acid gave a litre value of 35ml. The molarity of barium hydroxide solution was 12003) @ 014 — (6) 028 ©) 035) 007 6.02 = 10% molecules of urea are present in 100 ml of ts solution. The concentration of urea solution is [2002] (2004) (@) 002M (b) 0.01M (c) 001M (4) 01M (Avogadro constant, Nx =6.02 «1023 mot) Toneutralise completely 20 ml.of 0.1 M aqueous solution ‘of phosphorous acid (H,PO;), the value of 0.1 M aqueous KOH solution required is {2004} (@) 40m (b) 20mL (e) 10mL—(@) mL. The ammonia evolved from the treatment of 030 g of an ‘organic compound for the estimation of nitrogen was passed in 100 mL of 0.1 M sulphuric acid. The excess of acid required 20 mL of 0.5 M sodium hydroxide solution for complete neutralization. The organic compound is (2004) (@) urea (b) benzamide (©) acetamide (@) thiourea ‘Two solutions ofa substance (non electrolyte) are mixed in the following manner. 480 mil of I.5M first solution + $20 ml of 1.2.M second solution, What is the molarity ofthe final mixture? 2005) (@) 270M () 134M (©) 150M (@) 120M Ifwe consider that 1/6, in place of 1/12, mass of carbon atom is taken to be the relative atomic mass uni, the mass of one ‘mole ofthe substance will 12005] UL. Rn 2B. 4 18, 16. W. (a) bea function of the molecular mass of the substance (6) remain unchanged (©) increase two fold (d) decrease twice How many mole of magnesium phosphate, Mg,(PO,): will contain 0,25 mole of oxygen atoms? [2006] (@) 125«107 (b) 25% 107 (©) 002 (@ 3.125% 102 Density of a 2.05M solution of acetic acid in water is 1L02,gmL. The molality ofthe solution is 12006) (@) 228molke! (b) 0.44 mol ke! (©) 1.14molkgt (a) 328mol kg ‘The density ing mL~!) ofa 3.60 M sulphuric acid solution that is 29% 1,S0, (molar mass= 98 2 mol-") by mass wil be @ 145 (164 2007] () 188 @) 12 Inthe reaction, (2007) 2Al(S) + 6HCI(aq) > 2A1°*(aq) + 6CI”(aq)+3113() (@) 112 LHy(g) at STP is produced for every mole Haq) ‘consumed (6) 6 LHCI(aq) is consumed for every 3 1 H,(g) produced (©) 336LH,(g)is produced regardless of temperature and pressure for every mote A/ that reacts (@_ 67.2 Hyg) at STP is produced for every mole Al that reacts Consider the following reaction AMO," + COG +211" xMn?* +2yCO> + FH20 The value’s ofx, y and zin the reaction are, respectively [JE M2013] (@ 5,2and16 (b) 2,Sands (©) 2,Sand16 (@ 5,2and8 ‘A gaseous hydrocarbon gives upon combustion 0.72 g of water and 3.08 g of CO. The empirical formula of the hydrocarbon is [JE M2013] © CH, 0) GH, ©) CoH @) Cylly Experimentally it was found that a metal oxide has formula My 9g0. Metal M, present as M°* and M®* in its oxide Fraction ofthe metal which exists as M?* would be [JE M2013] (@) 508% (@) 701% —(b) 408% (©) 605%CHAPTER Structure of Atom I Section-a TITAS 3 5 Rts 1. Themass of hydrogen atom is. fine Marky 2. Isotopes ofan element differ in the number of | in their nuclei (1982-1 Mark) 3. When therearetwoelectrons in the same orbital, they have spins. (4982-1 Mark) 4. Elements ofthe same mass number but of different atomic numbers are known as (1983 - 1 Mark) ‘The uncertainty principle and the concept of wave nature of matter were proposed by and respectively. (Heisenberg, Schrodinger, Maxwell, de Broglic) (1988 - 1 Mark) 6. The light radiations with discrete quantities of energy are called (4993 - 1 Mark) 7. Wave functions of electrons in atoms and molecules are called (1993 - 1 Mark) 8 The 2p,, 2py and 2p. orbitals of atom have identical shapes but differ in their (1993-1 Mark) ‘The outermost electronic configuration of Cris (1994-1 Mark) 8 Rio 1. The outer electronic configuration of the ground state chromium atom is 344s, (4982-1 Mark) 2. Gamma raysare electromagnetic radiations of wavelengths of 10-em to 10-5 em, (1983 - 1 Mark) 3. Theenergy ofthe electron in the 3c-orbital is ess than that inthe ds-orbital inthe hydrogen atom. (1983-1 Mark) 4. Theelectron density in the X¥plane in 34,2 _ 42 otbital is 2200. (1986 - 1 Mark) 5. Inagivenlectric particlesare deflected more than ca-particles in spite of «-particles having larger charge (1993-1 Mark) c ERCreryeiconuss ‘The number of neutrons in dipositive zine ion with mass ‘number 70 is (979) @ 4 &) 36 © 8 @ 0 Rutherford’s experiment on scattering of a-particles showed forthe firsttime that the atom has (1981-1 Mark) (a) electrons (b) protons (c) nucleus Any p-orbital can accommodate upto (@)_ four electrons (b) sixelectrons (©) twoelectrons with parallel spins (@) two electrons with opposite spins The principal quantum number of an atom is related tothe (1983 - 1 Mark) (4) neutrons (1983 - 1 Mark) (@) size ofthe orbital (6). spinangular momentum (©) ambital angular momentum (@) orientation ofthe orbital in space Rutherford’ scattering experiment is related to the size of the (1983 - 1 Mark) (@)_ nucleus (6) atom (©) electron (@) neutron The increasing order (Jowest first) forthe values of e/m (charge/mass) for electron (e), proton (p), neutron (n) and alpha particle (a)is (1984-1 Mark) (a) e,p.na (b) m,p.ea (©) np.ae (d) n,a,pe Correct set of four quantum numbers for the valence (outermost) electron of rubidium (Z= 37) is (1984-1 Mark) @ 5,0,0,4% 0) 5.1.0,4% (©) 5,1,1,4+% (d) 6,0,0,+% Which electronic level would allow the hydrogen atom to absorb a photon but not to emit a photon? (1984-1 Mark) (@) 3 © 2 (&) 2p @ Is GP_302110, 1B. 4 16. n. ——___ Tropiie-wise Sotved Papers - CHEMISTRY ‘Bohr mode! ean explain (@) the spectrum of hydrogen atom only (b) spectrum of an atom or ion containing one electron only (ce) the spectrum of hydrogen molecule (d)_ the solar spectrum The radius ofan atomic nucleus is ofthe order of (1985-1 Mark) (a) 10cm (b) 10cm () 10cm (@) 10%cm Electromagnetic radiation wth maximum wavelength is (1985 - 1 Mark) (@) ultraviolet (©) radiowave (©) X-ray (@)_ infrared Rutherford’ alpha particle seatering experiment eventually Jed tothe conclusion that (1986-1 Mark) (a) mass and energy are related (b) electrons occupy space around the nucleus: (©) neutrons are buried deep in the nucleus (d)_ the point of impact with matter can be precisely determined Which one of the following sets of quantum numbers represents an impossible arrangement? (1986 - 1 Mark) loom Mm, ®3 2 2 ¥ (b) 4 oO 0 % @ 3 2 3 % @ 5 3 0 ” The ratio ofthe energy ofa photon of 2000A wavelength radiation tthat of 40004 radiation is: (7986-1 Mark) fa) % (b) 4 © % @ 2 The iad of nucle that is isotonic is (1985 - 1 Mark) (1988 - 1 Mark) Ue! Ng i @ CGN, GP (EC. GN, SF © CGN.GF @ Be. GN, SF ‘The wavelength of'a spectral line for an electronic transition is inversely related to (1988 - 1 Mark) (@)_thenumber of lectrons undergoing the transition (b) the nuclear charge of the atom (© the difference in the energy of the energy levels involved inthe transition (@ the elosty ofthe letron undergoing the transition ‘The rita diagram in which the Aulbou principles vilated is (1988-1 Mark) a » @ [N NYT (b) [Ft ttt © [N TTT 18, 19. 20, a 2. 2B. m4, 28, o WITT The outermost electronic configuration of the most cleetronegative element is (1988 - 1 Mark) ()_ ns? np? (b)_ ns? npt (©) ns? np* ()_ ns? mph The correct ground state electronic configuration of chromium atom is: (1989 - 1 Mark) (@) [Ar]3a4s! (b) [Ar3dast © [Ande (©) [Anda 4st ‘The correct set of quantum numbers for the unpaired clectron of chlorine atom is (1989-1 Mark) n 1 m @ 2 1 0 o 2 1 1 © 3 1 1 @ 3 0 0 Which of the following does not characterise X-rays? (1992-1 Mark) (a) The radiation can ionise gases (b) ecauses ZnS to fluorescence (©). Defected by electric and magnetic fields (@) Have wavelengths shorter than ultraviolet rays Which ofthe following relates to photons both as wave motion and asa stream ofparicles? (1992-1 Mark) (@) Inference (0) B=me? (©) Difaction (@) Ein A 3p orbital has (19955) (@)_ two non spherical nodes (b) two spherical nodes (©) one spherical & one non spherical node (@) one spherical and two non spherical nodes Theorbital angular momentum ofan electron in 2s orbitals: (1996 - 1 Mark) Lh a b) Ze @ +p () Zero h h © a) 2. oF @ a5 Forad-clectron, the orbital angular momentum is (1997-1 Mark) (@) Vo(h/2n) (©) V2(h/2) (©) (hi2m) (@ 20h/2m) ‘The electrons, identified by quantum numbers m and J, ()n=4,1= 1 (i) (il)n=3,1=2, and (v)n=3, T= | can be placed in order of increasing energy, from the lowest to highest, as (1999 -2 Marks) @) (—. This momentum for an s-cleetron will be given by {2003} h (a) zero (>) on h @ th © ae © +335 5 Which one of the following groupings represents a collection of isoelectronic species %(At. nos. : Cs : $5, Br:35) (2003) (a) N¥,F,Na* (b) Be, Al*,Cl- (© C#*,C',Br (@) Na", Ca, Mg In Bohr series oflines of hydrogen spectrum, the third line from the red end corresponds to which one ofthe following iner-orbit jumps ofthe cletron for Bohr orbits in an atom of hydrogen {2003}, @ $52 © 451 © 245 @ 352 The de Broglie wavelength ofatennis ball ofmass 60g moving with a velocity of 10 metres per second is approximately (2003) (@) 10>! metres (b) 10° metres (©) 10° metres (@) 10° metres Planck's constant, h=6.63 » 1043s, Which of the following sets of quantum numbers is correct foran electron in 4f orbital ? [2004]Structure of Atom 10, UL 4 18, 16. Consider the ground state of Cr atom (X=24), The number ofelectrons with the azimuthal quantum numbers, ¢= Land 2are, respectively [2004] (@ 16and4 (b) 12ands (©) Wanda (@ IGands ‘The wavelength ofthe radiation emitted, when ina hydrogen atom electron falls from infinity to stationary state 1, would be (Rydberg constant = 1,097%107 m!) 12004] (@ 406nm (b) 192m, © nm @ 9bd0%nm Which one of the following sets of ions represents the collection of isoelectronic species? [2004], (@)_K*.Cr, Mg, Sc (b)Nat,Ca*, So, (©) K*Ca,Se%,Cr —(€)_ Nat, Mg, AI, (Atomic nos. :F =9, C= 17, Na= 11, Mg= 12, AL= 13, K=19,Ca=20,Se=21) In a multi-electron atom, which of the following orbitals ‘described by the three quantum members will have the same ‘energy inthe absence of magnetic and electric fields? 12005), m=0 © n-2/=1m=1 © 0-3, @ Danae ©) (Chand) © @and©) (@ (And ®) OF the following sets which one does NOT contain isoelectronic species? 12008) @B) n=2,1=0, ©) n=3,/=2,m=1 m=0 (@ BO}”,CO},NO} (b) S03", CO}, NOZ © ONN,CH —— @ PO}, $0", C10; According to Bohr’s theory, the angular momentum of an electron in SY orbit is [2006] (@) 10h/x (b) 2Sh/x (©) Shin @ 10h/x Uncertainty in the position of an electron (mass = 9.1 107 kg) moving with a velocity 300 ms, accurate upto 0.001% willbe 20061, (@ 192%102m (©) 192*102m (b) 3.84% 102m (@ 576% 107m (h=6.63 « 10Js) Which one of the following sets of ions represents colletion of isoelectronic species? [2006] @ NOR FS (b) Li*,Na' Me, Cat (©) K*,Cr,Ca®*, Se (@)_ Ba®*, Sr*,K*, Ca? Wm. 18, 19. a 2. 2B. mM Which ofthe following sets of quantum numbers represents the highest energy of an atom? 12007) @ n=4,1=0,m=0,s=+172 Which one of the following constitutes a group of the isoelectronic species? {2008} (@) CH,07,C0,NO_— (0) NO*,C},CN-.N 2 (©) CN",N2,0} CF @)_Nz,03,NO*,CO The ionization enthalpy of hydrogen atom is 1.312 * 1083 ‘mol! The energy required to excite the electron inthe atom is (2008), (@ 851% 105Jmot (b) 656% 105J mot (©) 756% 1083mor! (a) 9.84 108 mot! Calculate the wavelength (in nanometer) associated with a proton moving at 1.0 * 10° ms~! (Mass of proton = 1.67 « 10-27 kgand h=6.63 * 10-5) (@) 040m () 25nm 12009], (© 140nm (@ 032mm In an atom, an electron is moving with a speed of 600 mis with an accuracy of 0.005%. Certainity with which the Position ofthe electron can be located is (h=6 6» 10k m?s-!, mass ofelectron, e Vkg): [2009], (@ 5.10107 m () 192% 109m (©) 384* 103m (@ 152 10-4m The energy required to break one mole of Cl Cl bonds in Cl, is242 kJ mol"! The longest wavelength oflight capable ofbreaking a single Cl ~Cl bond is fromn= ton. (c=3% 108 ms!andN,=602 «103 mol), (2010) (@) 594nm (b) 640nm (©) 700nm @) 494mm Tonisation energy of He’ is 196 » 10-¥ Jaton The energy ‘ofthe first stationary state (n=!) of L?*is [2010] (@) 4811016 Fatom! —(b) 4.41 10-7 Sater! (© 22 «10'S Satom-! 882% 10-17 Fatom-! ‘A gas absorbs a photon of 355 nm and emits at two ‘wavelengths. Ione ofthe emissions iat 680 nm, the other isat 011) (@ 103Snm © 761m (b) 325mm (@ 518mmory 25, Ihe electrons identified by quantum numbers m and ¢ ) n=, B) n=4, © n=3, (D n=3, can be placed in order of increasing energy as @ OCI>Br. (1993 - 1 Mark) 3. Thebasic nature of the hydroxides of group 13 (Gr. IB) decreases progressively down the group. (1993 - 1 Mark) [ell MCQs with One Correct Answer 1, Thecorrect order of second ionisation potential of carbon, nitrogen, oxygen and fluorine is (1981-1 Mark) @ C>N>0>F () O>N>F>C (© O>F>N>C @ F>0>N>c ‘The element with the highest first ionization potential is, (1982-1 Mark) (6) carbon (@) oxygen (@)_ boron (©) nitrogen 3. The first ionisation potential in electron volts of nitrogen and oxygen atoms are respectively given by (1987-1 Mark) @ 146,136 () 136,146 © 136,136 (@ 146,146 4. Atomic radii of fluorine and neon in Angstorm units are respectively given by (1987-1 Mark) (@ 072,160 (b) 160,160 © onon (@)_ None of these values ‘5. The electronegativity of the following elements increases inthe order (1987-1 Mark) (@) C.NSiP () NSLP (©) SiRCN (@ BSN 6. The first ionisation potential of Na, Mg, Al and Siare inthe order (1988 - 1 Mark) (@) NaAlMg>Al> (©) NaMg>Al50,>P,0 (6) CO,>N,0,>S0, (©) Na0>MgO>AL0, (@) K,0>Ca0>MgO 15, Amongst H,O, HS, H,Seand HyTe,theone withthe highest boiling point is (20008) (@) 1,0 because of hydrogen bonding (b)_ HyTe because of higher molecular weight (6) H,S because of hydrogen bonding (@ H,Sebecause of lower molecular weight 16, Identify the correct order of acide strengths of CO,, CuO, 20, 1,0 202s) @) CaOp 5 Oe 1. Arrange the following in (Decreasing ionic size : Ma2*, O%,Na', F (1985-1 Mark) (ii) Increasing acidic property : ZnO, Na,O,,P,0,,MgO (1985-1 Mark) (it) Increasing fist ionization potential : Mg, Al Si, Na (1985-1 Mark) (iv) Increasing size: CI-,S*,Ca*, Ar (1986-1 Mark) (©) Increasing order ofonie size: N'-, Na*, FO, Mg (1991-1 Mark) (Increasing order of basic character : MgO, SrO, KO, Ni0,Cs,0 (1991-1 Mark) (ott) Arrange the following ionsin order of their increasing radii: Lit, Mg, K*,AD* 2. The first ionization energy of carbon atom is greater than that of boron atom whereas, the reverse struc forthe second ionization energy (1989 -2 Marks) BH RCs 1, Read the following statement and explanation and answer as per the options given below ASSERTION : The first ionization energy of Be is greater than that of B. (20008) REASON : 2p orbital is lover in energy than 2s (@)_Ifboth assertion and reason are CORRECT, and reason isthe CORRECT explanation ofthe assertion (b) Ifboth assertion and reason are CORRECT, but reason isNOT the CORRECT explanation ofthe assertion (6). Ifassertion is CORRECT, but reason is INCORRECT. (@)_Ifassertion is INCORRECT, but reason is CORRECT, 1 ERR 1. Among the following, the number of elements showing only ‘one non-zero oxidation state is O,CLEN,P.Sn, TI, Na, TL (1999-3 Marks) (2010)Classification of Elements and Periodicity in Properties ________________@ 4 [| Section-6 STS eIWATT3 1. According tothe Periodie Law of elements, the variation in properties ofelements is related to their 12003) (@)_ nuclear masses (0) atomic numbers (©) nuclear neutron-proton number ratios (@) atomic masses 2. Which one ofthe following isan amphoteric oxide? @ Nao (0)S0, 12003] © BO, @z00 3. Which one ofthe fllowing ions has the highest value of ionic radius? 2004) @ & @ Be © ui @ & 4. Among Al,0,,Si0,,P,0, and SO, the correct order of acid strength is 12004] (a) Al,0, Mg? > Nat > F>0% (0) Na >Mg* > At > 0% > F (©) Na* > Fo > Mg** >? > al () 0% > F > Nat > Mg** > A Which one of the following orders presents the correct sequence ofthe increasing basic ature ofthe given oxides? 011) @)_AlO) (©) _N: pyramidal, sp?, B: planar, sp? (@)_N: pyramidal, sp°, B tetrahedral, sp? Identify the least stable ion amongst the following (2002S) @) Lr (b) Be) B @c Which of the following molecular species has unpaired -electron(s) ? (2002S) @N OF © OF (@) OF Which ofthe following ae isoelectronic and isostructural? NO;-,CO,*,C10;-,$0, (20038) (0) 80,.NOy (@) NO;.CO2” (©) C0;,coe (@) CO}-S0, According tomolecular orbital theory which ofthe following statement about the magnetic character and bond order is correct regarding 03 2004s) (@) Paramagneticand Bond order <0, (6) Paramagnetic and Bond order > 05 (©) Diamagneticand Bond order O, Which species has the maximum number of lone pair of electrons on the central atom? (20055) (a) [COP (b) XeF, (c) SF, @ Or Among the following, the paramagnetic compound is 2007) (a) Na,0, © NO ©) 0 @ Ko, S51. The species having bond order different from that in CO is 2007) @ NO WN ON WN ‘Assuring that Hund’s rule is violated, the bond order and magnetic nature ofthe diatomic moleculeB, is (2010) (@) Land diamagnetic (b) O.and dimagnetic (©) Land paramagnetic (4) Oand paramagnetic 53. The species having pyramidal shape is. e201) @ SO; () BF, © Siof (A) OSF, Geometrical shapes ofthe complexes formed bythe reaction of Ni* with CI-,CN“and H,O, respectively, are (2011) (@)_ octahedral, tetrahedral and square planar (6) ‘tetrahedral, square planar and octahedral (©) square planar, tetrahedral and octahedral (@ octahedral, square planar and octahedral Assuming 2-2p mixing is NOT operative, the paramagnetic species among the following is (DEE Ads, 2014) @ By OB ©) @N The geometries of the ammonia complexes of Ni? Pe and Zn** respectively are (IEE Ads 2010) (@) octahedral, square planar and tetrahedral (6). square planar, octahedral and tetrahedral (©) tetrahedral, square planar and octahedral (4) ctahodral, tetrahedral and square planar D BRC 4 58 1. CO,isisostuctural with (1986-1 Mark) @ HCl, () SAC, © C. (@ No, ‘2. The linear structure is assumed by (1991 - 1 Mark) @ SC, (b) NCO (CS, @)_ NOP 3. Which of he following have identical bond order? (1992-1 Mark) @ & 60; | wWCN 4. ‘Themolecules that will have dipole moment are (1992-1 Mark) (@) 2,2-dimethylpropane (b) txans-2-pentene (©) cis-3-hexene (@) 2233Hetramethytbutane 8. Thecompound(s) with TWO lone pairs of electrons on the central atom itare) (EE Ads. 2016) @ BF, (6) CIF, © Xr, @) SF, 6. According to Molecular Orbital Theory, (JEE Ad 2016) (@) CE isexpected tobe diamagnetic (©) OF? isexpected tohavea longer bond length than O, (©) Nj and Nj have the same bond order (8) He has the same energy as two isolated He atoms 5 Bie 1. Water isliquid while 1, isa gas at room temperature, (1978) 2. Write the Lewis dot structural formula for each of the following. Give, also, the formula of neutral molecule, which has the same geometry and the same arrangement of the bonding electrons as in each ofthe following. An example isgiven below in the case of H,O* Ho H H:0:H, HEN:H, Lewis dot Neutral structure molecule SVEN (ivy NCS (1983-1<4=4 Marks) 3. Howmany sigma bonds and how many pi-bonds re present ina benzene molecule? (1985-1 Mark) 4. Write the Lewis dot structure ofthe following 0,,C0Cl, (1986-1 Mark) 5. Arrange the following ()Nj,0,,F,,Cl, in inereasing order of bond dissociation energy. (1988-1 Mark) (i Increasing strength of hydrogen bonding (X-H-X) (1991-1 Mark) 0,S,R.CLN (ii)_Inthe decreasing order ofthe © - bond length present inthem (2004-4 Marks) 0, KO, and 0, [ASF] 6. Thedipole moment of KCI is 3 336 » 102% Coulomb meters ‘hich indicates that it is a highly polar molecule. The interatomic distance between K"* and Clin tis molecule is 2.6 «10"?m,Caleulate the dipole moment of KCI molecule if there were opposite charges of one fundamental unit located ateach nucleus. Calculate the percentage ionic character of ka. (1993-2 Marks) 7. Using the VSEPR theory, identify the type of hybridization and draw the structure of OF, What ae the oxidation states of Oand F? (1994-3 Marks) 8. A.compound of vanadium has a magnetic moment of 1.73 BM, Work out the electronic configuration of the vanadium {on inthe compound (1997-2 Marks) 9. Interpret the non-linear shape of H,S molecule and non- planar shape of PCI, using valence shell electron pair repulsion (VSEPR) theory. (Atomic numbers: H=1,P=15, S=16,CI=17) (1998- 4 Marks) 10, Write the MO. electron distribution of O,. Specify its bond order and magnetic property (2000-3 Marks) 11. Using VSEPR theory draw the shape of PCL, and BrF, (2003-2 Marks) 12, Drawthe structure of XeF, and OSF, according to VSEPR theory, clearly indicating the state of hybridisation ofthe central atom and lone pair of electrons (ifany) on the central atom. (2004-2 Marks) Bal Match the Following ‘Match the orbital overlap figures shown in List-I with the description given in Listll and select the correct answer using the code given below the lists. (JEE Adv. 2014) Topic-wise Solved Papers - CHEMISTRY Litt p—dzamtibonding d—dobonding Ce a p—dxbonding eo o8 s 4 d-deantibonding Code, Po oQ@ RS (a) 2 13 4 m4 3 1 2 @2 3 1 4 @ 4 13002 BH RSs 1. Read the following Assertion and Reason and answer as per the options given below (1998 - 2 Marks) 3@ Avert The cetonic arte 0,” \y ° neon: PA, sci it loved et srando Sat Scand (a) Ifboth assertion and reason are correct, and reason is emer (b)_ Ifboth assertion and reason are correct, but reason is Sere eames (9 Waneunis ctetin ators (d)_Ifassertion is incorrect but reason is correct. 2. Cale bite aston wd feos tera per the options given below: (1998 - 2 Marks) Rata fing ebay scombereomrere fucon avons eee ipl wai (a) Ifboth assertion and reason are correct, and reason is. tana opbeaiatac aaraon (b) Ifboth assertion and reason are correct, but reason is. eee (c) Ifassertion is correct but reason is incorrect. (@)_ Ifassertion is incorrect but reason is correct. 1 Eee 1. Based on VSEPR theory the number of 90 degree F-Br-F angles in Br is (2010) 2 Thetotal number oflone-pairs of electrons in melamine is (JEE Adv. 2013)Chemical Bonding and Molecular Structure. —____________» Ais of species having the formula XZ, is given below. XeF 4, SFy, SiFy, BFy-, Br, [Cu(NH,),?*, [FeCl [CoC and [PCL Defining shape on the bass ofthe location of X and Z atoms, the total numberof species having a square planar shape is (SEE Adv. 2014) 4 ea ‘Among the triatomic moleculeslions, BeCl;, N3 , N,O, NO$,0s,SCly, Cp, 15 and XeF, the total number of linear molecule(sVion(s) where the hybridization of the central atom does not have contribution from the d-orbitals) is [Atomic number: = 16, CI=17,1=53 and Xe= 54] (JEE Ad. 2015) Section-B JIT OW 73 Inwhich ofthe following species the interatomic bond angle is 109°28"? [2002] @ NH, Bry" (b) (NH)', BE, (©) NH,,BF, (@) (NHL). BFy ‘Which ofthe following are arranged in an inereasing order oftheir bond strengths? 12002) @) Of <0,<0,"<0;7" (6) 0,-<0, <0, <0," (©) Oy <032-<0, <0," (A) 0,'<0,<0, <0; Hybridisation of the underline atom changes in: (@) AIH changes to AI (6) HO changes to H,0" (©) Nils changes to NH (@ inall cases ‘An ether is more volatile than an alcohol having the same molecular formula. This isdueto 12003) {@) alcohols having resonance structures (6) inter-molecular hydrogen bonding in ethers (©) inter-motecular hydrogen bonding in alcohols (@) dipolar character of ethers Which one ofthe following pairs of molecules will have permanent dipole moments for both members? [2003] (@)_ NO, andCO, (b) NO, andO, (©) SiF,andCO, (@) SiF,andNO, Which one of the following compounds has the smallest bond angle in its molecule ? 12003) (@) OH, —(b) SH, (©) NH, (@) SO, ‘The pair of species having identical shapes for molecules of both species is 12003) (@) XeF,,CO, (b) BF, PCI, (©) PRUE, (@) CF,SF, The correct order of bond angles (smallest first in H,S, NH, BF, and Sill is [2004] (@) HSNO* @ 0,50, Which ofthe following hydrogen bonds is the strongest? 12007) (@) O-H---F (b) O-H---H (©) F-H---F (@ O-H---0, Which one of the following pairs of species have the same bond order? 12008), (@ CN-andNO* () CNrand cn (© 03 andcn- (@) NO* and CNY The bond dissociation energy of B-F in BF, i646 kI mot whereas that of CF in CF, is $15 kJ mol! The correct reason for higher B-F bond dissociation energy as compared tothatofC- Fis {2008} (@)_ stronger « bond between Band F in BF as compared tothat between Cand F in CF, (©) significant pr—pr interaction between Band Fin Bs ‘whereas there is no possibility of such interaction between C and Fin CF. (©) lower degree ofp interaction between Band Fin BB, than that between Cand F in CF, (@) smaller sizeof B-atom as compared tothat of C-atom Using MO theory, predict which of the following species has the shortest bond length? 12008) @ 0} 0; © oF @ OF Among the following the maximum covalent characteris shown by the compound 011) @ FeCl (b) SnCl (©) AIC — @) MgCl The hybridization of orbitals of N atom in NO; ,NO3* and NH, are respectively pou (@)_sp, sp*, sp? (b) sp*, sp, sp? (© 5, sp, sp (2) sp, sp*, sp The structure of IF, is rou) (@)_ square pyramidal (b) trigonal bipyramidal (©) octahedral (@) pentagonal bipyramidal Ortho-Nitrophenol is less soluble in water than p- and m- Nitrophenols because (2012) (@)_o-Nitrophenol is mote volatile steam than those of m- ‘and peisomers (6) o-Nitrophenol shows intramolecular H-bonding (©). o-Nitrophenol shows intermolecular H-bonding (@)_ Melting point of o-Nitrophenol is lower than those of ‘m-and p-isomers, 28, In which of the following pairs the two species are not isostructural ? [2012] (@) CO} and NOS (b)_ PCI; and Sic, (©) PFsand BrP; (@ AIR} and SF, 29, Which one ofthe following molecules is expected to exhibit diamagnetic behaviour ? [JEEM2013} @ & ) Ny © 0} (@) Sy 30, Which of he following isthe wrong statement ? [JEEM2013] (a) ONC] and ONO are not isoelectronic. (b) Oymolecule is bent (c) Ozone is violet-black in solid state (d) Ozone is diamagnetic gas. 31. _Inwhich ofthe following pais ofmolecules/ons, both the species are not likely to exist? (IEE M2013] (=) H3,He} () 1 ,He} (© HRHey (Hye? 32. Stability of the species Lip, Lij and Lif increases in the order of: (JEEM2013] @ Lip 2 1273 © 5 © 53°20 The temperature at which a real gas obeys the ideal gas laws over a wide range of pressure is (1981-1 Mark) (@) Critical temperature (6). Boyle temperature (©) Inversiontemperature (d) Reduced temperature The ratio of root mean square velocity to average velocity ofa gas moleculeat a particular temperature is (1981-1 Mark) (@) 1086:1 (6) 1:1086 (©) 2:1086 (@) 1086-2 elim atom is two times beaver than a hydrogen molecule. ‘A1298 K, the average kinetic energy ofa helium atom is (1982-1 Mark) (@)_twotimes that ofa hydrogen molecule. (b) same as that ofa hydrogen molecule (©) four times that ofa hydrogen molecule. (@)_halfthat ofa hydrogen motecule Equal weights of methane and hydrogen are mixed in an empty container at 25°C. The fraction ofthe total pressure exerted by hydrogen is (1984-1 Mark) 1 8 @ 5 5 1 16 5 Oi Rate of diffusion ofa gas is (@) directly proportional to its density. (6). directly proportional to its molecular weight (©) directly proportional tothe square root of its molecular weight (@ inversely proportional to the square root of its molecular weight The average velocity ofan ideal gas molecule at 27°C is 0.3 imise. The average velocity at 927°C wil be: (1986-1 Mark) (@) 06misee (6) 03misee (©) 0.9misee (@ 30misee Tn an der Waals equation of state for a non-ideal gas, the term that accounts for intermolecular forces is (1988-1 Mark) (1985 - 1 Marky @ (vb) () Rr oy © (r+3) @ «ry GP_302110, ML. 2. 3B. M 18, 16. —_ Tropiie-wise Solved Papers «CHEMISTRY A battle of dry ammonia and a bottle of dry hydrogen chloride connected through a long tube are opened simultaneously t both ends the white ammonium chloride ring first formed wil be (1988-1 Mark) (@) atthe centre ofthe tube (6) ear the hydrogen chloride bot. (©) near the ammonia bottle (@) throughout the length ofthe tube. The values of van der Waals constant a’ forthe gases O;, 1N,, NHL and CH, ae 1360, 1390, 4.170 and 2.253 L? atm rot respectively. The gas which can most easly be liguified is (1989-1 Mark) (a) 0, (b) Ny (©) NH, @) CH, ‘The density of neon will be highest (1990 - | Mark) @ st () oc24m (©) 273°C, Latm. (d)_ 273°C, 2atm. ‘The rate of diffusion of methane at a given temperature is ‘twice that ofa gas X. The molecular weight of Vis (1990-1 Mark) (@ «0 ) 320 © 40 @ 80 According tokinetic theory of gases, fr a diatomic molecule (1991-1 Mark) (@) the pressure exerted by the gas is proportional to mean velocity ofthe molecule (©) the pressure exerted by the gas is proportional tothe Foot mean velocity ofthe molecule (©) the root mean square velocity of the molecule is inversely proportional tothe temperature (6) themean translational kinetic energy ofthe molecule is proportional tothe absolute temperature Atconstant volume, for afixed number of moles ofa gas the pressure ofthe gas increases with rise in temperature du to (1992-1 Mark) (@) Increase in average molecular speed (b) Increased rate of collisions amongst molecules (©) Inerease in molecular attraction () Decrease in mean free path Longest mean free path stands for (1998S) (a) H, (b) Ny © 0 @ a, ‘Arrange the van der Waals constant fr the gases (19955) 1 Calg A 0217 Te GiHGCHyy) B 5464 Ml Neg C1800 NV. HO, D. 24060 @ FAIDIC IVE (© EC,IED,I-A,IVeB (&) ED IAB IV-C (@ FBILCIEAIVD wv. 19. 20, 2 2. 25, ‘The ratio between the root mean square speed of H, at SOK and that of, at 800 Ki, (1996-1 Mark) @ 4 (b) 2 @ 1 @ 14 X mL of H, gas effuses through a hole in a container in $ seconds. The time taken for the effusion ofthe same volume of the gas specified below under identical conditions is (1996-1 Mark) (@) 10 seconds: He (6) 20se0onds:0, (©) 2Sseconds: CO (@ 55seconds: CO, One mole of N,O,(g) at 300 K is kept in a closed container under one atmosphere. It is heated to 600 K when 20% by mass of N,O, (g) decomposes to NO,(g).The resultant pressure is (1996 - 1 Mark) @ 12am () 24am (©) 20am (@ Loam The compressibility factor foran ideal gas is (1997-1 Mark) @ 15 ®) 10 © 20 @ © A gas will approach ideal behaviour at (1999-2 Marks) (@)_lowtemperature and low pressure (b) low temperature and high pressure. (6) high temperature and low pressure. (@) high temperature and high pressure. The ms velocity ofhydrogen is y7 times he ms velocity of nitrogen. IF is the temperature of the gas, then (20008) @ THN) (0) TUH,)> TN) (© TUH)224 ites ©) Vy< 224 ites (©) Vi=224 litres (@ Vi=448iitres ‘At 100°Cand I atm, ifthe density ofiquid water is 1.0 gem? and that of water vapour is 0.0006 g em then the volume occupied by water molecules in I litre of steam at that temperature is 2000s) (@) 6om’ (b) cm (©) 06en* (@) 06cm? The root mean square velocity of an ideal gas at constant pressure varies with density (@) as 20018) @ @ 4 © Va @ Wa Which ofthe fllowing volume (V)- temperature (7) plots represcns the behaviour of one mle ofan ideal gas at one atmospheric pressure ? (2002S)States of Matter 2. 28. 29, 31. [-" 81, 373K) L__ yr) vy (2861, 373K) () 22a | ) six vay 3061, 373K) © @ af 273K) L__.rx) vy Te (L373) ‘When the temperature isinereased, surface tension of water (20025) @ (@) increases (b) decreases (©) remainseonstant (@)_ shows irregular behaviour Positive deviation from ideal behaviour takes place because of (20035) {@) Molecular interaction between atoms and PVinkT> 1 (b) Molecular interaction between atoms and PVink <1 (©). Finitesize ofatoms and PVinRT> 1 (4). Finite size ofatoms and PVink< 1 Theroot mean square velocity of one mole of monoatomic sashaving molarmass MisUjq,. Therelation between the average kinetic energy (E) of the g28 and tpg (20048) 3B aE 2M ® 3M © Hens =f57 @ viens = The ratio of the rate of diffusion of helium and methane under identical condition of pressure and temperature will @) ems Yems = be (20055) a4 b 2 1 @ 05 When one mole of monoatomic ideal gas at TK undergoes. adiabatic change under a constant external pressure of 1 atm volume changes from 1 litre to 2 litre, The final temperature in Kelvin would be (20055) Tr 2 (2) 3am (by + F<0.0821 2 (or (ay T = 50.0821 32, Amono-atomic ideal gas undergoes a process in which the ratio of P to V at any instant is constant and equals to 1 ‘What is the molar heat capacity of the gas @ # () 2R (2006-3M;-) 5R @ 0 o> ‘The term that corrects forthe attractive forces present in @ real gas in the van der Waals equation is, @ nb OO) = (2009 -3M; 1) © -Tr @ -nb For one mole of a van der Waal’s gas when 6 = 0 and T=300K, the PV vs, 1/V plot is shown below. The value of the van der Waal’s constant a (atm. liter? mol?) is 2012) = m1 Pv¢iteratm 0 20 30 1/V¢mol liter”) (@) 10 © 45 (b) 15 @ 30 ‘The qualitative sketches I, I and IIT given below show the variation of surface tension with molar concentration of three different aqueous solutions of KCI, CH,OH and CH,(CH,),,OSO; Na’ at room temperature. The correct assignment ofthe sketches is (EE As. 2016) I Mm m Surface tension Sunfice tension Consenaton Concenaion Coneenraton (@) KCL I:CHOH IM: CHYCH,,,080,-Na* (©) 1:CHYCH,,,0SO-Ne" I:CHOH —ML-KCL (©) I:KCL M:CHyCH,),OSO;Na’ Ill: CH,OH (@ 1:CHOH KCL IN: CHYCH,),,080,-Na*fry D Eee 1, When an ideal gas undergoes unrestrained expansion, no cooling occurs because the molecules : (1984-1 Mark) (@)_areabove the inversion temperature (b) exert no attractive forces on each other (©) dowork equal to loss in kinetic energy (@) collide without loss of energy 2. Ifa gasis expanded at constant temperature (@) the pressure decreases (1986-1 Mark) (b)_thekineticenergy of the molecules remains the same (©). thekinetic energy of the molecules decreases (@ the number of molecules ofthe gas increases 3. Equal weights ofethane and hycrogen are mixed in an empty. container at 25°C. The fraction ofthe total pressure exerted by hydrogen is (1993 - 1 Mark) @ 1:2 ® i © 1:16 @ 15:16 4. According to Graham's aw, ata given temperature the ratio ofthe rates of diffusion r/r, of gases A and B is given by (1998-2 Marks) @) Py )(M Mg)! (b).(My/My) (PP y)!2 (©) (PyP_(MyM,)"? — (d) (M,/M,) (Pi) (Where P and M are pressures and molecular weights of| gases Aand B respectively.) Refer tothe figure given (2006- 5M;—1) Which ofthe following statements is wrong? (a) For gas A,. and Z will linearly depend on pressure (b) Forgas, 6=0.and2 wil linearly depend on pressure (©) Gas C is a real gas and we can find ‘a’ and “6° if intersection data is given (@ Alvan der Waal gases will behave like gas C and give Positive slope at high pressure 6. A.gas described by van der Waals equation — (2008-1 Mark) (@) behave similar toan ideal gas inthe limit oflarge molar volumes (6) behaves similar to an ideal gas is in limit of large pressures 2 —_ Tropiie-wise Solved Papers «CHEMISTRY (©) ischaracterised by van der Waals coefficients that are dependent on the identity of the gas but are independent ofthe temperature (@) has the pressure tha is lower than the pressure exerted by the same gas behaving ideally According to kinetic theory of gases (2) collisions are always elastic (b)_ heavier molecules transfer more momentum tothe wall, ‘of the container (©) only a small number of molecules have very high velocity (@)_between collisions, the molecules move in straight lines with constant velocities eau ‘One mole of a moneatomic real gas satisfies the equation p(V — b) = RT where b is a constant. The relationship of interatomic potential V(r) and interatomic distance r for the 228s given by (WEE Ad. 2015) ve) o| @ 7 vo 2 r ) vo y Tr © Vo] | - dd)States of Matter, ——_______ eo Bteeuckeroru Calculate density of NH, at 30°C and 5 atm pressure. (1978) 3.7 gofa gasat25°C occupied the same volume as0. 184g of hydrogen at 17°C and at the same pressure. What is the ‘molecular weight ofthe gas? (1979) ‘A straight glass tube has two inlets and Yat two ends. The length of tube is 200 em, HCI gas through inlets Xand NH, ‘gas through inlet Yare allowed to enter the tube atthe same time. What fumes appear at point P inside the tube. Find distance of P from X. (1980) 1 litre of mixture of CO and CO, is taken. The mixture is passed through tube containing red hot charcoal. The vvlume now becomes 1.6 litre. The volumes are measured ‘under the same conditions. Find the compesition of mixture by volume (1980) ‘At room temperature, ammonia gas at | atm pressure and hydrogen chloride gas at Patm pressureareallowed toefiuse through identical pinholes from opposite ends ofa glass tube of one metre length and of uniform cross-section, Ammonium chloride is first formed ata distance of 60 em from the end through which HCI gasis sent in, What is the value of P? (1982-4 Marks) Calculate the average of kinetic energy, in Joules of the moleculesin 8.0 gofmethane at 27°C, (1982-2 Marks) Oxygenis present in | lite flask ata pressure of 7.6 = 10-19 1mm of Hg, Calculate the number ofoxygen molecules inthe flask at °C (1983 -2 Marks) ‘When 2 gm of. gas Ais introduced into an evaluated flask kept at 25°C, the pressure is found to be one atmosphere. If 3 am of another gas B is then added tothe same flask, the total pressure becomes 1.5 atm. Assuming ideal gas behaviour, calculate the ratio of the molecular weights My: Mp (1983-2 Marks) Calculate the root mean square velocity of azone kept in a closed vessel at 20°C and 82 em mercury pressure (1985-2 Marks) Aspherical balloon of 21 em diameter is tobe filled up with hydrogen at NTP. fom acylinder containing the gas at 20 atmospheres at27°C. Ifthe eylinder ean hold 2.82 litres of ‘water, calculate the number ofalloons that canbe filled up (1987 § Marks) ‘The average velocity at 7K, and the most probable velocity at TK of CO, gas is9.0 * 10* em sec! Calculate the value of T, and, (1990-4 Marks) Calculate the volume occupied by 5.0 g of acetylene gas at 50°Cand 740 mm pressure (1991 - 2 Marks) ‘At27°C, hydrogen is leaked through atiny hoe into vessel for 20 minutes. Another unknown gas at the same ‘temperature and pressure as that of H, is leaked through the same hole for 20 minutes. After the effusion ofthe gases the mixture exerts a pressure of6 atmosphere. The hydrogen content of the mixture is 0.7 mole. Ifthe volume of the MW 19. 2. container is 3 litres, what is the molecular weight of the unknown gas? (1992 - 3 Marks) Atroom temperature the following reactions proceed nearly tocompletion (1992-4 Marks) 2NO+0,->2NO,->N;O, The dimer, N,O,, solidifies at 262 K. A250 ml flask and a 100 ml flask are separated by a stop-cock. At 300 K, the nitric ‘oxide inthe larger flask exerts a pressure of 1.053 atm, and the smaller one contains oxygen at 0789 tm, The gases are mixed by opening the stopcock and after the end of the reaction the flasks are cooled at 220K, Neglecting the vapour pressure ofthe dimer, find out the pressure and composition ‘ofthe gas remaining t 220 K, (Assume the gases to behave ideally) ‘A gas bulbof | litre capacity contains 2.0 x 10?! molecules ‘of nitrogen exerting a pressure of 757 10 Nnv, Calculate the root mean square (¢m.s) speed and the temperature of the gas molecules. Ifthe ratio ofthe most probable speed t0 ‘the root mean square speed is 0,82, calculate the most probable speed for these molecules a this temperature. (1993-4 Marks) A4: | molar mixture of He and CH, is contained in a vessel at 20 bar pressure . Due to a hole in the vessel, the gas mixture leaks out. What is the composition of the mixture ceffusing out initially? (1994 - 2 Marks) An LPG (liquefied petroleum gas) eylinder weighs 14.8 kg ‘when empty. When full, it weighs 29.0 kg and shows a pressure of 5 atm. Inthe course of use at 27°C, the weight ‘of the fll eylinder reduces to 23.2 kg, Find out the volume ‘of the gas in cubic meters used up at the normal usage conditions, find the final pressure inside the eylinder. ‘Assume LPG to be r-butane with normal boiling point of| oc (1994-3 Marks) ‘A mixture ofethane (CH,) and ethene (C,H,) occupies 40 Iitresat 1,00 atm and at 400 K. Themixture reacts completely with 130 g of O, to produce CO, and H1,0. Assuming ideal gasbehaviour, calculate the mole factions of CH, and C,H, inthemixtue (1995-4 Marks) Thecompostion ofthe equilibrium mixture( Cla =* 2C1), ‘which is attained at 1200°C, is determined by measuring the rate of effusion through a pin-hole, It is observed that at 1.80 mmllg pressure, the mixture effuses 1.16 times.a fast as krypton effuses under the same conditions. Calculate the faction of the chlorine molecules dissociated into atoms (Relativeatomicmassofkr=84.) (1995-4 Marks) ‘A 20.0 em! mixture of CO, CH, and He gases exploded by an electric discharge at room temperature with excess of ‘oxygen. The volume contraction is found to be 13.0¢m?. A further contraction of 14.0 em? oceurs when the residual asi treated with KOH solution. Find out the composition ofthe gaseous mixture in terms of volume percentage. (1995-4 Marks) An evacuated glass vessel weighs 50.0 g when empty, 148.0 sgwhen filed with aliquid of density 0.98 gm! and 50.5 ger ‘when filled with an ideal gas at 760 mmHg at 300K. Determine the molar mass ofthe gas (1998 3 Marks) 22. The degree of dissociation is0 4a 400 K and 1.0 atm forthe gaseous reaction PCI, <== PCI, + Cl,. Assuming ideal behaviour of all gases, calculate the density of equi mistureat 400 K and atmosphere. (Relative atomic mass of P=31.0andCl=35.5) (1998 - 3 Marks) 23, Using van der waal’s equation, calculate the constant, ‘a’ ‘when two moles of a gas confined ina four ltr flask exerts a pressure of 11.0 atmospheres at a temperature of 300 K, The value of bis 005 L mot! (1998- 4 Marks) 24, Forthe reaction, N,O,(@) > 2NO,(e)+0.5O,(g), calculate the mole fraction of N,O,(g) decomposed at a constant ‘volume and temperature ifthe initial pressure is600 mm Hg and the pressure at any time is 960 mm Hg, Assume ideal gas behaviour (1998 - 3 Marks) 28. One mole of nitrogen gas at 0.8 atm takes 38 s to diffuse through a pinhole, whereas one mole of an unknown compound of xenon with flourine at 1.6 atm takes 57's to diffuse through the same hole. Calculate the molecular formula of the compound. (1999 -5 Marks) 26, The pressure exerted by 12 g ofan ideal gas at temperature PC in a vessel of volume V litre is one atm, When the temperature i increased by 10 degrees atthe same volume, the pressure increases by 10%, Calculate the temperature ¢ and volume ¥. (Molecular weight ofthe gas= 120.) (1999 -§ Marks) F Eo Fy __ Topiic-wise Sotved Papers - CHEMISTRY 27. Calculate the pressure exerted by one mole of CO, gas at 273 K ifthe van der Waal's constant a = 3.592 dm atm ‘mol. Assume that the volume occupied by CO, molecules isnegligible (2000-2 Marks) 28, The compression factor (compressibility factor) for one mole ofa van der Waals gas at0°C and 100 atmospheric pressure is found to be 0.5. Assuming that the volume of a gas ‘molecule is negligible, calculate the van der Waals constant a. (2001-5 Marks) 29, The density ofthe vapour ofa substance at | atm pressure and 500 K is 0.36 kg m". The vapour effuses through @ small hole at arate of 133 times faster than oxygen under the same condition (2002-5 Marks) (@)_ Determine (molecular weight, (Gi) molar volume, ii) compression factor (Z) of the vapour and iy) which forces among the gas molecules are dominating, the atractve or the repulsive? (b)_ Ifthe vapour behaves ideally at 1000 K, determine the average translational kinetic energy of a molecule. 30, Theaverage velocity of gas molecules is 400 misee. Calculate itsrms velocity atthe same temperature. (2003-2 Marks) 31. Agraph is plotted between PY,, along Y-axis and P along X-axis, where Vis the molar volume of areal gas. Find the intercept along Y-axis, (2004-2 Marks) ‘Each question contains statements given in two columns, which have (o be matched. The statements in Column-I are labelled A, B, C and D, while the statements in Column-II are labelled p, 4, r, s and Lae ees 1 Any given statement in Column. can have correct matching with ONE OR MORE statemeni(s)in \(QQOOO Set Deepak gir 2900 Fe dg dbs tenia cmerinings, — ‘|PROOO ‘bubbles will look lke the given 1. Match gases under specified conditions listed in Column I with their properties/Iaws in Column IL Indicate your answer by darkening the appropriate bubbles ofthe 4 » 4 matrix given in the ORS, Column t (A) Hydrogen gas (P=200 atm, 7=273K) (B) Hydrogen gas (P~0,7=273K) © ©0,(P=1atm,7=273K) (D)_Real gas with very large molar volume fel Comprehension Based Questions and ¥ are two volatile liquids with molar weights of 10 gmol"! and 40 g mol”! respectively. Two cotton plugs, one soaked in X and the other soaked in Y, are simultaneously placed at the ends ‘of a tube of length L = 24 em, as shown inthe figure. The tube is filled with an inert gas.at | atmosphere pressure and a temperature ‘0f300 K. Vapours of and ¥ react to form a product whichis frst (2007) Column It (©) Compressibility factor 1 (@) Attractive forces are dominant (@) PV=nRT (9)_PW=nb)= nT. ‘observed ata distance dem from the plug soaked in X. Take Xand to have equal molecular diameters and assume ideal behaviour for the inert gas and the two vapours. ms A__i oh. Cotton wool ——>" ‘Cotton woo! soaked in 2 ¢ itil formation soaked in ¥States of Matter 1. Thevalueofd in em (shown in the figure, as estimated from Graham’slaw, is (JEE Adv. 2014) @ 8 ®) 2 © 16 @ » 2. The experimental value of dis found to be smaller than the estimate obtained using Graham’slaw. This is due to (EE Adv, 2014) (@) Larger mean free path for X'as compared to that of Y (b) Larger mean free path for Yas compared to that of X (©) _ Increased collision frequency of ¥ with the inert gasas ‘compared to that of X'with the inert gas (@) Increased collision frequency of X withthe inert gasas ‘compared to that of ¥ with the inert gas Assertion & Reason Type Questions 1. Read the following statement and explanation and answer as per the options given below Assertion : The value of van der Waals'constant ‘is larger for ammonia than for nitrogen. Reason : Hydrogen bonding is present in ammonia, (1998-2 Marks) (@)_Ifboth assertion and reason are correct, and reasons the correct explanation ofthe assertion (b) Ifboth assertion and reason are correct, but reason is not the correct explanation ofthe assertion. (©) Ifassertion is correct but reason is incorrect. (@) assertion is incorrect but reason is correct, Read the following statement and explanation and answer as per the options given below Assertion : The pressure ofa fixed amount ofan ideal gas is proportional toits temperature Reason : Frequency of collisions and their impact both increase in proportion tothe square root of temperature. (20008) (@)Ifboth assertion and reason are CORRECT, andreason is the CORRECT explanation ofthe assertion (b) Ifboth assertion and reason are CORRECT, but reason isNOT the CORRECT explanation ofthe assertion (©) Ifassertion is CORRECT, but reason is INCORRECT, (@)_Ifassertion is NCORRECT, but reason is CORRECT, 1 ERR At 400 K, the root mean square (rms) speed of a gas X (molecular weight = 40) is equal tothe most probable speed ofgas Vat 60 K. Themolecular weight ofthe gas Vis (2009) ‘Toan evacuated vessel with movable piston under external pressure of 1 atm, 0.1 mol of He and 1,0 mol ofan unknown compound (vapour pressure 0.68 atm. at0°C) are introduced. Considering the ideal gas behaviour, the total volume (in litre) ofthe gases at 0°C isclose to oi ‘The diffusion coefficient of an ideal gas is proportional to itsmean fee path and mean speed. The absolute temperature of an ideal gas is increased 4 times and its pressure is increased 2 times. As a result, the diffusion coefficient of this gas increases x times. The value of x is JEE Ad 2016) I Section-B UC mi 1. For an ideal gas, number of moles per litre in terms ofits pressure P, gas constant R and temperature Tis (@ POR (b) PRE 12002) (© PRT @ ROP, 2. Value of gas constant R is 12002) (@) 0082liteam (b) 0.987 ca md-! K-! (© 833 mor! K+ (@)_83ergmot! K! 3. Kinetic theory of gases proves eet ees (b) only Charles” law (©) only Avogadro's law (@ Allofthese. 4. According to the kinetic theory of gases, in an ideal gas, between two successive collisions a gas molecule travels (@)_ ina wavy path [2003] (©) imastraight line path (©) with an accelerated velocity (@) inacircular path Aste temperature is raised from 20°C to 40°C, the average kinetic energy of neon atoms changes by a factor of which ofthe following ? 2004) 12002] 313 @ () 137253) © @2 Ivar der Waals equation ofstate ofthe esa, the constant bY isameasure of 12004] {@) volume occupied bythe molecules (b) intermolecular attraction (©) intermolecular repulsons (@) intermolecular colisions per unit wolume Which one ofthe following statements is NOT true about the effect of an inrease in temperature onthe distribution of molecular speeds ina gas? 12005) (@)Thearea under the distribution curve remains the same asunder the lower temperature (b) The distribution becomes broader (©) The fraction ofthe molecules withthe most probable speed increases (8) The most probable speed increases If 10- dim’ of water i introduced into a 1.0 dm? flask at 300 K, how many moles of water are in the vapour phase ‘when equilibrium is established? 2010](Given » Vapour pressure of H,O at 300 K is 3170 Pa; R=8314IK-! mol!) (@) 556+ 10 mol (©) 153 «102 mol (©) 446% 102mol ——(@) 127% 10° mol 9. ‘a°and‘b’are van der Waals’ constants for gases. Chlorine ismore easily liquefied than ethane because [2011] (@) and b for Cl, > aand b for CH, (0) and for Cl; b for CH (@) afor Cl, > a for Cyt, butb for Cly NaCl © Cy* Or) COr) () Nyed+3Hye)-r2NHYe) ®) 372 @ +743 3. The AH? forCO,(g), CO(g) and H,0(g) are -393 5,110.5 and -241.8 kJ mol"! respectively. The standard enthalpy change (in kJ forthe reaction CO,(g)+ H,(@) -» COCg)+ H0()is (20008) (@) SAL () 412 (©) 2625 @ 12 4. In thermodynamics, a process is called reversible when (20018) (@) surroundings and system change into each other. (b) there ismo boundary between system and surroundings. (©) the surroundings are always in equilibrium with the system. (@ the system changes into the surroundings spontaneously. 5 JEE Advanced/ IIT-JEE Which one ofthe following statements is false? (@) Work isa state funetion (0) Temperature i asate function. (©) Change inthe state is completely defined when the initial and final tates arespecitied (8) Work appears atthe boundary ofthe system One mole of a non-ideal gas undergoes a change of state (20a1m, 301, 95(K)-> (40am, $01, 245K) with achange ‘ninteral energy, AU = 30.0 Latm. The change in enthalpy (tt) ofthe process in L atm is (20028) fa) 40.0 () 23 (c) 440 (d)_ not defined, because pressure is not constant Which ofthe eacton defines aH; ? ems, (@) (diamond) *O2(2) —+ CO) 20018) 1 1 ©) ZHae) +7 Fe) — He (©) Nag) +3H aig) —2NH x) ot (8) CO%p) +5 0x8) ‘Two moles of an ideal gas is expanded isothermally and reversibly ffom 1 litreto 10 litre at 300K. The enthalpy change >COr¢) (in kd) for the process is (20045) @ Mae () -1140 © OW (@ 430 The enthalpy of vapourization of liquid is 30 kJ mol! and entropy of vapourization is 75 3 mol" K, The boiling point ofthe liquid at I atm is (20045) (@) 250K (b) 40K (©) 450K (@) 60K Theditect conversion of Ato Bis difficult, hence itis carried cut by the following shown path c——» | | Given A B AS.4-sc) = 50 €41, AS(c-p) = 30 eu, ASip-4p) = 20 eu, where e.u. is the entropy unit, then AS) is (2006 - 361,-1) @ *0eu (&) +00eu (©) eu (@ -100eu. GP_3021er) 1 __ Topiic-wise Sotved Papers - CHEMISTRY The value of logy K for areaction A —— Bis Given : A, Hog =-54.07 KI mol", 4,S3o¢x. 10 IK! mol! and 314 JK"! mot! 2007) () 10 @) 100 For the process H,O(1) (1 bar, 373 K)—> H,0( (1 bar, 373 XK), the correct set of thermodynamic parameters is (2007) @) AG=0,AS=He ——(b) AG=0, AS=-ve © AG=4e,AS=0 —— (@) AG=—Ve, AS=+e The pecies which by definition has ZERO standard molar enthalpy of formation at298 Kis 2010) @) Br(e) () Chi © 1,0@) ©) Cys) The standard enthalpies of formation of CO,(), HyO() and lucose(s) at 25°C are 400 kl/ml, 300 kfimol and 1300 i/mol, respectively, The standard cialpy of combustion per gram of glucose at 25°C is (JEE Advanced 2013-0) (@) +2900K) (6) 290% © -I611K (@) #6118 For the process (JEE Ad, 2014) H0() > H,0¢g) at T= 100°C and | atmosphere pressure, the correct choice is (9) AS yy? 9 AS rcings = (©) ASyacm > 08M AS ermine <2 ©) ASsiem “0 ANd AScrountings = 2 @ sree <0 and aS yee <0 ‘One mofe ofan ideal gas at'360 Kin thermal contact with surroundings expands isothermally for 1.0 Lto20Lagainst constant pressure of 3.0 atm. In this proces, the change inentropy of surroundings (AS) in JK! is (Lam =1013)) (GEE Ads. 2016) (@) 5763 () 108 © 1013 (@) $763 D BRR eee [Identify the intensive quantities from the following: (1993-1 Mark) @) Enthalpy (b) Temperature (©) Volume (@), Refractive Index The fllowingis (are) endothermic reation(s) (@) Combustion of methane (1999-3 Marks) (&) Decomposition of water (©) Dehydrogenation of ethane to ethylene (@ Conversion of graphite to diamond ‘Among the following the state function(s) is(are) (2009) (@) Internal energy (6)_Ieversible expansion work (©) Reversible expansion work (@) Molar enthalpy ‘Amongthe following, the intensive property is (propertiesare) (2010) (@) molar conductivity (b) electromotive force (©) resistance {(@) heat capacity For an ideal gas, consider only P-V work in going from an initial state X tothe final state Z. The final state Z.can be reached by either of the two paths shown in the figure. Which ofthe following choice(s) is (are) correct? [Take AS as change in entropy and was work done], (2012) Prarmosphen Vitro) Seay t MS y42 Meo ‘The reversible expansion of an ideal gas under adiabatic and isothermal conditions is shown in the figure. Which of the following statement(s) is (are) correct ? (Py VT) isothermal adiabatic 7 @ 1-1 2012-1) &) T,>7, (©) Wigenermal > "adiabatic (0) AO rina > ACriabac Anideal gis aa thermallynsltd vesel at interalpessre volume = Vand absolute temperature=T, expands ireresbly against zero external pres, a sown i the diagram, The final internal pressure, volume and abecute temperature of the eas are P, V3 and T respectively, For thisexpansion, GEE Ads, 2014) Pa=0_| nengle J rT haves Thema natin @ 90 ©) TT) (©) PAVy=P\V, (@) PV; 5 Es The enthalpy for the following reaction (AH") at 25°C are given below (1981 - 2 Marks) O FHW+ FO, > ONG) 1006 Kea (i) Hy) > 2M) 104.18 keal Gi) Og) > 208) 118.32 keal Calculate the O-H bond energy in the hydroxyl radical.‘Thermodynamics, —________ 38 10, uw The molar heats of combustion of C,H), Clgraphite) and (gare 31062 keal, 94.05 kel and 6832 keal, respectively. Calculate the standard heat of formation of C,H,(g). (1983-2 Marks) The heat energy, g, absorbed by @ gas AH, is true at what condition(s). (1984-1 Mark) Given the following standard heas of reactions (i)heat of formation of water=~68.3 kcal, (ipheat of combustion of acetylene =~310.6 eal; (iipheatof combustion of ethylene =-337 2 kal, Caleulate the heat of reaction for the hydrogenation of acetylene at constant volume (25°C), (1984-4 Marks) The bond dissociation energies of gaseous HCl, and HCL are 104, $8 and 103 kcal/mole respectively. Caleulate the enthalpy of formation of HClgas. (1985-2 Marks) The standard molar heats of formation of ethane, carbon dioxide and liquid water are -21.1, 94,1 and -68.3 keal respectively. Calculate the standard molar heat of combustion of ethane (1986-2 Marks) An ntimate mixture of feric oxide, Fe,0,, and aluminium, AA, isused in slid el rockets, Caleuate the fuel value per ram and el value perce ofthe mixture: Heats of formation and densities are as follows (1988-2 Marks) 1,(A1j0,)= 399 keamole; Hj(Fej0,)= 199 keallmole, Density of Fe,05= 52 glee; Density of Al=2.7 glee. Anathlete is given 100 gm of glcuose (CHO, ofenergy equivalent to 1560 kl, He utilizes $0 perent ofthis gained energy in the event. In order to avoids storage of energy in the body, caloulate the weight of water he would need to perspire. The enthalpy of evaporation of water is 44 KI/ mmol. (1989-2 Marks) The standard enthalpy ofeombustion at 25°C of hydrogen, cyclohexene (Clq) and eyelohexane (Cell) are -241, ~3800 and~3920 kifmole respectively Calculate the heat of hydrogenation of eyelohexene (1989 2 Marks) Using the data ll value ae in keal mol“ at 25°C) given below, calculate the bond energy of C-C and C-H bonds. (1990-5 Marks) AHP ombuston(@thane) 20 AE gntsion PFOPRME) 53900 Ao) + a Bond energy of HHH 040 Alt ofH,0() 680 AIF of CO,(@) 940 A gas mixture of 3.67 litres of ethylene and methane on complete combustion at 25°C produces 6.11 litres of CO, Find out the amount ofheat evolved on burning one litre of the gas mixture, The heats of combustion of ethylene and ‘methane are—1423 and-891 kJ mot"! at25°C, (1991-5 Marks) 2 18. 16. Determine the enthalpy change ofthe reaction C3HHg(g) + Hy(g) > CH (g) + CH), at 25% using the given heat of combustion values under standard conditions Compound —Hy(@)—CHy(g) C3HG(g) Clgraphite) AIP(kdimol) 2858 9900-15600 -3935 The standard heat of formation of CyHy(g)is~103.8ki/mol (1992-3 Marks) In order to get maximum calorific output, a burner should have an optimum fuel to oxygen ratio which correspondsto 3 times as much oxygen as is required theoretically for complete combustion ofthe fuel. A burner which has been adjusted for methane a fuel (with x litrefhour of CH, and 6x litzethour of O;) isto be readjusted for butane, C4Hyo. In ‘order to get the same calorific output, what should be the rate of supply of butane and oxygen ? Assume that losses due to incomplete combustion, etc, are the same for both the fuels and the gases behave ideally. (1993 - 3 Marks) Heats of combustion (CH, = 809 kI/ mok;CyHyo = 2878 kJ/mol The polymerisation of ethylene to linear polyethylene is represented by the reaction (1994-2 Marks) nCH2= CH, —+ CH) -CH2 4 where n has large integral value. Given that the average enthalpies of bond dissociation for C= Cand C-C at 298K are + $90 and + 331 kJ mol”, respectively, calculate the enthalpy of polymerisation per mole of ethylene at 298 K. The standard molar enthalpies of formation of cyclohexane(Djand benzene) at 25°C are 156 and +491) mol! respectively: The standard enthalpy ofhydrogenation of eyclohexene(/) a 25°C is—119 kl mol. Use these data to estimate the magnitude of the resonance energy of benzene, (1996 - 2 Marks) Compute the heat of formation of liquid methy! alcoho in Kilojoules per mole, using the following data. Heat of ‘vaporization of liquid methy alcohol = 38 kl/mol. Heat of formation of gaseous atoms from the elements in their standard states, H, 218 kUimol,C, 715 mol, 0,249 /mok Average bond energies C—H=415kt/mo,C- Anhydrous AICI, is covalent. From the data given below, predict whether it would remain covalent or bocome ionic in aqueous solution. (Ionsation energy for Al = $137 KI mol!; AHpydration for AY =—4665 kJ mol; AHpydration for C-=-381 kJ mol!) (1997-2 Marks) From the following data, calculate the enthalpy change for the combustion of eyclopropane at 298 K. The enthalpy of| formation of CO,(2), H,0() and propene(g) are ~ 393.5, = 285.8 and 20.42 kJ mol"! respectively. The enthalpy of isomerisation ofeyeloprepane to propene is— 33.0 kJ mot! (1998 5 Marks)red 19. Eximat the average S-F bond enery’in SF The values of standard enthalpy of formation of SF,(g), S(e)and F(g) are :~ 1100, 275 and 80 kJ mot~' respectively. (1999-3 Mark) 20, A sample ofargon gas at | alm pressure and 27°C expands reversibly and adiabatically from 1.25 dm? to 2.50 dm’. Calculate the enthalpy change inthis process. Cy, fo argon is 12.48 JK~! mot (2000-4 Marks) 1 21. Show that the reaction CO(g}+-5O2()—> CO>() at 300 K, is spontaneous and exothermic, when the standard ‘entropy change is~0,094 kJ mol! K-!. The standard Gibbs five energies of formation for CO, and CO are~394 4 and =137.2kl mob! respectively. (2000-3 Marks) 22, Diborane is a potential rocket fuel which undergoes combustion according othe reaction. (2000-2 Marks) Balle (g)* 30, (8) > B,0,(5)*311,0(8) From the following dat, calculate the enthalpy change for the combustion of diborane 20(5)+303(¢) 98,0366) AH=-127345 mot! Hy(g)*403(g)—>H:0(0) aH=-286KI mot"! 1,01) —> H,0(¢) AH=44kI mot"! 2B(s)+3H2(g)—> B,Hg(g) AH=36kI mot! When I-pentyne (A) is treated with 4 N alcoholic KOH at 175° it sconverted slowly intoan eqlirium mixture of 1.3% |-pentyne (A), 95.2% 2-pentyne (B) and 3.5% of 1, 2- pentadiene (C). The equilibrium was maintained at 175°C. CaleuateAG° forthe following equltia B= Cc acy 2. BA act From the caleulated value of 4G) and aG% indicate the order of stability of (A), (B) and (C). Write a reasonable m4, 25, 26. 2. __ Topiic-wise Sotved Papers - CHEMISTRY Two moles of a perfect gas undergo the following processes (2002-5 Marks) (a) _areversible isobaric expansion from (1.0 atm, 20.0L) to (10atm, 40.01), (b) a reversible isochoric change of state from (1.0 atm, 40.0 L)to(0.S atm, 40.01), (©) areversible isothermal compression fom (0S atm, 40.0 L)to(1.0 atm, 20.0L). (Sketch with labels each of the proceses on the same P-V diagram. (i) Calculate the total work (w) and the total heat change (q) involved in the above processes. What wil be the values of AU, AH and AS forthe overall process? C, value of He is alvays 3R/2 but C, value of H is 3R/2at JowtemperatureandSR/2 at moderate temperature and more than SR/2 at higher temperature explain in two to three lines. (2003-2 Marks) ‘An insulated container contains 1 mol ofa liquid, molar volume 100 ml, at 1 bar. When liquid is steeply pressed to 100 bar, volume dereases 099 ml. Find, AH and AU forthe process (2004-2 Marks) Inthe following equilibrium N,O,(g) —* 2NO,(g) (2004 - 2 Marks) When $ moles of each i taken and the temperature is kept at 298 K, the total pressure was found tobe 20 bar Given: aG#(N30,) = 100k}; AG}(NOs)= 50 kd (0) Find AG ofthe reaction at 298 K (i) Find the direction of the reaction Forthe reaction, 200 +0; —» 200; AH =-S60k), Two ‘moles of CO and one mole of O, are taken in a container of| volume 1 L. They completly form two moles of CO, the gases deviate appreviaby ftom ideal behaviour. If the pressure in the vessel changes from 70 to 40 atm, find the reaction mechanism showing all intermediates leading to magnitude (absolute vale) of AUat S00 K (I Lat =01 ky) (&).@)and(C). (2001 10 Marks) (2006-6M) F Er 9 DIRECTION (Q. 1 & 2): Each question contains statements given in two columns, which have to be ‘matched. The statements in Column-I are labelled A, B, C and D, while the statements in Column-II —— are labelled, q 1 sand. Any given statementin Column-can have correct matching with ONEOR — \(O@OO@ ‘MORE statement) in Columnll. The appropriate bubbles corresponding tothe answers to these 3 Hon emt ch ie ce 09@09 Af the correct matches are A-p, s and t; B-q and r; C-p and q; and D-s then the correct darkening of rl]O®@OOO dnubbes will lok like the given 1. Match the transformations in column with appropriate options in column It (a) Colum-t (A) COz(s) > COz(g) B)_CaCOs(s) + CaO{s) +CO2(8) © 2Wo1L@ ©) Pott oid) > Ped, sti) Columa-tt (P) phase transition (@)__allotropie change (Allis positive (5) ASis positive () ASisnegativeThermodynamics 2. Match the thermodynamic processes given under Column-I with the expressions given under Column-L Column-t (A) Freezing of water at273 K and 1 atm O} (®) Expansion of I mol ofan ideal gas into a vacuum under isolated conditions @ (©) Mixingofequal volumes of two ideal gases at constant temperature and pressure) inan isolated container (©) Reversibleheating of Hg at stm fm 300K 10600 K, followed by reversible co) ‘cooling to 300K at 1 atm co Eeitiioemirekn: ns. {A fixed mass’m’ ofa gas is subjected to transformation of states from K to L to M (oN and back to K as shown in the figure Pressure (JEE Ad. 2013) 1, The succeeding operations that enable this transformation of sates are (@) Heating, cooling, heating, cooling (©) Cooling, heating, cooling, heating (©) Heating, cooling, cooling, heating (8) Cooling, heating, heating cooling ‘The pair of isochorie processes among the transformation of states is (@ KtoLandLtoM — (b) LtoMandNtoK (©) LtoMandMtoN — (@) MtoNandNtok 5 Erne Read the following statement and explanation and answer as per the options given below Assertion : The heat absorbed during the isothermal expansion ofan ideal gas against vacuum is zero. Reason : The volume occupied by the molecules ofan ideal gasis zero, (20005 (@)_Ifboth assertion and reason are CORRECT, and reason is the CORRECT explanation ofthe assertion, (b) 1Pboth assertion and reason are CORRECT, but reason isNOT the CORRECT explanation ofthe assertion 2 (JEE Adv. 2015) aG=0 (6) Ifassertion is CORRECT, but reason is INCORRECT. (@)_Ifassertion is INCORRECT, but reason is CORRECT, Statement - 1: There is a natural asymmetry between, converting work to heat and converting heat to work and Statement - 2 : No process is possible in which the sole result is the absorption of heat form a reservoir and its ‘complete conversion into work, (20085) (@) Statement-1 is True, Statement-2is True; Statement-2 isacorrect explanation for Statement-1 (b) Statement is True, Statement-2is True; Statement-2 isNOT acorrect explanation for Statement-1 () Statement is True, Statement-2 is False (@) Statement-1 is False, Statement-2is True roar) Tnaconstant volume calorimeter, 3 5 gofa gas wth molecular ‘weight 28 was burnt in excess oxygen at 298.0 K. The temperature ofthe calorimeter was found to increase from 298.0 K 0298.45 K due tothe combustion process. Given thatthe heat capacity ofthe calorimeter is 2.5 kJ K™!, the numerical value forthe enthalpy of combustion of the ens inkl mois (2009-6) One mole of an ideal gas is taken from a to b along two paths denoted by the solid and the dashed lines as shown inthe graphs below. Ifthe work done along the solid line path, and that along the dotted ine pth is wy then the integer closest tothe ratio w/w, is 2010) cam ob ds1b 2b 25 30 3 th ds sods aery [I Section-6 {TOIT Ian endothermic reaction is non-spontaneous at freezing point of water and becomes feasible at its boiling point, then ©) ai ise, as isthe (b) ay and as both are Hye (© aH and as both are—ve (@ aw istve, as is-ve Aeat engine abosrbs heat Q, at emperatureT, and heat Q, at temperature 7;, Work done by the engine is J (Q, + Q,). This data 12002] (@)_ violates 1*law of thermodynamics (©) violates 1* law of themodynamies iQ i (©) violates 1* law of thermodynamics of Q,is—ve (@)_ does not violate 1 law of themodynamics. 12002] ve 3. Forthereactions, 12002] 2C+0, 920, ; AH =.3935 2Zn+0, > 2200; AH =.4125 (@) carbon can oxidise Zn (©) oxidation of carbon isnot feasible (©) oxidation of Zn isnot feasible (@ Zncan oxidise carbon. 4. The heat required to raise the temperature of body by 1 Kis called [002], @) specific heat (©) thermal capacity (©) vaterequivalent —(@)_none ofthese. The internal energy change when a system goes from state A {0B is40 kiimole. thesystem goes fom AtoBbya reversible path and returns to state by an irreversible path what would be the net change in internal energy? 12003], @ > (40K (©) Zero d) 40kI fat 298 K the bond energies of C—H,C—C, C=C and Ht —Hbondsare respectively 414, 347, 615 and 435 KI mol", the value of enthalpy change forthe reaction H,C= CH,(g)+H3(g) > HxC—CH, (g)at298K will be 12003] (@) 25015 (+1251 (© =125%5 (@) +2500 7. _Inan reversible process taking plae at constant Tand Pand in which only pressure-volume wok s bing done, the change in Gibbs fee energy (4G) and change in entropy (8), satis the criteria (2003) @) (S)yg>0.(dG),p<0 (0) US) ¢=0, (4G), p= 0 (©) CS)y_=0,(dG)zp>0 (4) (AS)q, p <0, (AG)y p <0 8 10. rs __ Topiie-wise Sotved Papers - CHEMISTRY ‘The correct relationship between free eneray change in a reaction and the corresponding equilibrium constant K, is [2003] (@ -AaG=RTInK, (b) AG=RTIMK, (©) -AG=RTInK, — (@)-AG=RTInK, ‘The enthalpy change for a reaction does not depend upon 12003] use of different reactants forthe same product the nature of intermediate reaction steps the differences in initial or final temperatures of involved substances (@) the physical states of reactants and products An deal gas expands in volume from 110-0 1 = 10°? mat 300 K against a constant pressure of 1x10 Nm’?, The work @ © © done is [2004] (@ 270K (b) — 900% (©) -900 (a) 90018, The enthalpies of combustion of carbon and carbon ‘monoxide are ~ 393.5 and~283 kJ mol" respectively. The enthalpy of formation of carbon monoxide per mole is (@) -6165K5 () 6765K [2004], (© 105k (@ -105KI Consider an endothermic reaction X > Y with the activation energies Ey and Ep for the backward and forward reactions respectively. In general [2005], (@) there is nodefinite relation between Ey, and Ey ©) By a © Ey>Er @) Ey 2NH carried outat constant temperature and pressure, If AH and AU are the enthalpy and internal energy changes forthe reaction, which of the following expressions is true? 2005) (@ AH>au (b) aH (all diatomic molecules) are inthe ratioof 1: 1 :0.S and AH, for the formation of XY is ~ 200 kJ mole“!. The bond dissociation energy of X2 will be {2005} (@) 400k mol (b) 300K) mot! (©) 200k) mol (@) 100K mol”!‘Thermodynamics. —_______s 15, 19. 20. ‘An ideal gas is allowed to expand both reversibly and irreversibly in an isolated system. If T, is the initial temperature and, isthe final temperature, which ofthe following statements is correct? 12006), @ Mev= Tee (6) T,=T, for both reversible and irreversible processes. © Cx Tey (8) T,>T, foe reversible process but T= process The standard enthalpy of formation (AM) at 298 K for methane, CH,(g)is74 8 kI mol. The additional information required to determine the average energy for (C=H bond formation would be 12006), (@) the first four ionization energies ofcarbon and electron gain enthalpy of hydrogen (©) the dissociation energy of hydrogen molecule, Hy (©) the dissociation energy of H, and enthalpy of sublimation of earbon (@ latent heat of vapourization of methane The enthalpy changes forthe following processes ae listed below 12006), for irreversible Clfg)92C@), 242.3 mot Le) 21), 150K mot ICKg)>1(@)+Cl(@, 211.3kI mol" 1,6) +L), 276K mot! Given thatthe standard states for iodine and chlorine are 1,(¢)and C(), the standard enthalpy of formation fer Cg) is 2006) (@) +168kImo (b) 42448kd mor (©) 146k mot (@) 168k mor" {(AH—AU) for the formation of arbon monoxide (CO) from itselements at 298 Kis 0061, (R=83145K" mot!) (@) -24757)mot! ——(b)_ 2477573 mol (©) -1238.78Jmor? ——(@)_1238.78 Jmol" Inconversion of lime-stone tolime, CaCO, (5) > CaO(s) +CO, (g) the valuesof AH® and 4° are+179,1 ki mol! and 160.2.K respectively at298 K and 1 bar. Assuming that AH® and AS? donot change with tem- perature, temperature above which conversion of limestone tolime will be spontancous is 12007) (@ 118K (b) 108K, (©) 1200K @ MK Assuming that water vapour is an ideal gas, the internal energy change (AU) when 1 mol of water is vapourised at 1 bar pressure and 100°C, (given : molar enthalpy of vapourisation of water at I bar and 373 K=41 kJ mol and R=83J mot! K") willbe 12007] (@)_ 41.0045 mot (b) 4.1004 mot! (©) 37904kImot! (@37.904KI mot" a 2. 25, 26. 639 Identify the correct statement regarding spontancous pro- cess: 12007] (@) Lowering of energy in the process isthe only eriterion for spontaneity For a spontaneous process in an isolated system, the change in entropy is positive. (©) Endothermie processes are never spontaneous. (@)_Exothermie processes are always spontaneous. Oxidising power of chlorine in aqueous solution can be determined by the parameters indicated below. © Jai? x? Fence) cr) tinal cr (aq) Casing the data, 349 kJ mol", uml, = 2401 mot, 8 42 yall =-381 KI mol, wb (2008) (a) +152kJmor! (b) -610kJ mor! (c) -850kI mol! (@) +120k mot! Standard entropy ofX, Y, and X Y, are 60, 40 and 503K"! ‘mot-! respectively For the reaction, 1,3 xj alle 30 fteteer e temperature willbe 12008] @) 1250K (b) 500K (©) 750K (@) 100K, On the basis of the following thermochemical data ("Hag = 12009] HO()) > H*(aq)+ OH” (aq); AH = 57.32K) Hg(g)+ $02(@) —91,0(0, all=286 2044 ‘The value of enthalpy of formation of OH" ion at 25°C is: (@) 228885 (b) 42288810 © 38S2k (@) 288K The standard enthalpy of formation of NH, is —46.0 ki mot" Ifthe enthalpy of formation of 1 from its atoms is~436KJ mol and that of N, is—712 kJ mot, the average bond enthalpy of NH bond in NH is [2010] (@) -964kmot" (0) +352KImot (©) +1056KI mot" (@ —1102% mor! Fora particular reversible reaction at temperature 7, Hand AS were found to be both #ve. I 7, is the temperature at eilibrium, the reaction would be Spontaneous when 2010] @ 127 © TisStimesT (b) T>T, @ Ttor a. 28. 29, _ Tropiie-wise Solved Papers «CHEMISTRY The entropy change involved in the isothermal reversible expansion of 2 mole ofan ideal gas from a volume of 10 toa volume of 100 dm? at 27°C is: [201] (@) 3834mot!K! ——(b)_35.8Jmot! Kt (b) 323%mortK! — (@) 42.35 mot KA ‘The incorrect expression among the following is: [2012] AG, jystem ASwtat @ (©) In isothermal process, rane =-ART end are=Tas* RT A piston filled with 0.04 mol of an ideal gas expands reversibly fom 50.0ml-to375 mL ataconsan temperature F370. Asitdoesso,it absorbs 208 ofheat The valves of and forthe proces al be REM 2013] (R=8.314 Jmol K) (In 7.5 =2.01) ©@ mn @ K=esoRe 3 (@) q=+208J,w=-208) (b) q=-208J,w=~208) (©) q==2083,w= +2085 (8) q=+2081,w= +2083 For complete combustion of ethancl, CHsOH (1) +302 (8) —+2C0» (g)+3H,0(1), the amount of heat produced as measured in bomb calorimeter, is 1364.47 kJ mol"! at 25°C, Assuming ideality the enthalpy of combustion, 4H, for the reaction will be: (Re8314kI mo") [EE M2014), (@) -136.95 kI mot (b)_=1361.95 ks mol (©) -1460.95 kJ mot (a) 1350.50 ks mol" The heats of combustion of carbon and carbon monoxide are 393.5 and -283.5 kJ mot", respectively, The heat of formation (in kd) of carbon monoxide per mole is [JEE M2016), (@ -6%5 (©) M05 (b) -1105 @ 66SCHAPTER Equilibrium | ccc JEE Advanced/ IIT-JEE FA Fillin the Blanks 1. Theconjugate base of HS0; in aqueous solution is (1982-1 Marky 2, Amelement which can exists positive ion in acidic solution and also as a negative ion in basic solution is said to be (1984-1 Mark) 3. Fora given reversible reaction ata fixed temperature, equilibrium constants K,,and Kare related by. (1994-1 Mark) 4. A ten-fold increase in pressure on the reaction, 'No(g)+3H2(g) —=2NH(g) atequilibrium results in ink (1996 - 1 Mark) Inthe reaction “+1, > 15, the Lewis acid is (1997-1 Mark) 8 RE 1. Aluminium chloride (AICI, isa Lewis eid because it ean donate electrons (1982-1 Mark) 2. Tfequiibrium constant forthe reaction A, +B = 2AB, is, K then forthe backward reaction AB f= sA, + By the equilibrium constants 11K (1984-1 Mark) 3. When a liquid and its vapour are at equilibrium and the pressure is suddenly decreased, cooling oocurs (1984-1 Mark) Solubility of sodium hydroxide inereases with increase in temperature (1985 15 Mark) c ERC nue 1. Molten sodium chloride conducts electrcitry due to the presence of (1981-1 Mark) (@) free electrons (b) fice ions (©) freemolecules (@) atoms of sodium and chlorine 2. An acidie buffer solution can be prepared by mixing the solutions of (1981-1 Mark) (@)_ ammonium acetate and acetic acid (6) ammonium chlorideand ammonioum hydroxide (©) sulphuric acid and sodium sulphate (@), sodium chloride and sodium hydroxide The pH1 ofa 10-* molar solution of HCl in water is (1981-1 Mark) @ 8 © -8 (6) between 7 and 8 (@) between 6 and 7 The oxidation of SO, by O; to SO, isan exothermic reaction. Theyield ofSO, willbe maximum if (1987-1 Mark) (@) temperature is increased and pressure is kept constant (6) temperature is reduced and pressure is increased (6) both temperature and pressure are increased (@), both temperature and pressure are reduced For the reaction (1981-1 Mark) HyJg)+I,(e) 2H) the equilibrium constant K, changes with (@) total pressure (6) catalyst (©) the amounts of H, and I, present (@ temperature Of the given anions, the strongest Bronsted base is (1981-1 Mark) @ CO () Clo; © a0; @ a0; At 0°C, pure water has [H,0"] 10° mole litre!. What isthe value of K,,at 90°C? (1981-1 Mark) @ 106 ©@ The precipitate of CaF (K,,=1.7 10°) {obtained when equal volumes ofthe following are mixed (@) 104M Ca?*+ 104M (b) 102M Ca? + 10M (©) 10-SMCa*+10MF (d) 10M Ce + 10M liquid isin equilibrium with its vapour at its boiling point On the average the molecules in the two phases have equal (1984-1 Mark) (6) potential energy (0) kinetic energy ®) 10? @ 10 (1982-1 Marky (@) inter-molecular forces (©) total energy GP_3021cn 10. 4 1”. 19. 20, __ Topiie-wise Sotved Papers - CHEMISTRY ‘Pure ammonia is placed in a vessel ata temperature where its dissociation constant (a) is appreciable, At equilibrium (1984-1 Mark) (@)_K, does not change significantly with pressure. (©) does not change with pressure (©) concentration of NH does not change with pressure (@ concentration ofhydrogen is less than tat ofnitrogen, ‘A certain buffer solution contains equal concentration of X- and HX. The K; for X-is 10". The pH of the buffer is @ 4 () 7 (1984-1 Mark) © 0 @ 4 certain weak acid has dissociation constant of 1.0% 10% ‘The equilibrium constant for its reaction with a strong base is (1984-1 Mark) @ 10104 &) 10x10" (©) 1.010! (d) 1.0« 10! An example ofa reversible reaction is: (1985 - I Mark) (@)PO(NO,),aq + 2Nal(aq) —> Pbl,(s)+2NaNO.(aq) (b)_-AgNO,(aq)+ H1CKaq) > AgCI(s)+ NaNO,(aq) (©) 2No(s)*H,0(0 > 2NaOH(aq) +H (@) (8) KNO 4) + NaCKaq)—> KCI(aq)+ NaNO fea) Thebes indicator for detection fend pont in tation of a weak acid and a strong base is (1985 - 1 Marky (@)_ methyl orange 3104) (b) methyl red (5106) (©) bromathymol blue (6107 5) (@)_phenolphthalein (8 to 9.6) The conjugate acid of NH} is (1985-1 Mark) @ Ni (0) NHOH (© NBG © NH “The compound that is not a Lewis acid is (@ BF, (b) AICI, (©) BeCl, (d) Sac, ‘The compound insoluble in acetic acid is: (1986-1 Mark) (@) calcium oxide (6) calcium carbonate (©) calcium oxalate (d) calcium hydroxide The compound whose 0.1 M solution is basic is (1986 - 1 Mark) (@) ammonium acetate (6) ammonium chloride (c) ammonium sulphate (d)_ sodium acetate ‘When equal volumes ofthe following solutions are mixed, precipitation of AgCl (K,= 1.810") will occur only with (@)_104M(Ag*)and 104 M(Cr) (1988 - 1 Mark) (b) 10M (Ag") and 10-5 M(C) (©) 10°M(Ag*)and 10°°M (Cl) (@) 10M (Ag*)and 10° M (Cr) The pK,, of acetylsalicyclic and (aspirin) is 3.5. The pH of gastric juice in human stomach is about 2-3 and the pH in the small intestine isabout 8. Aspirin willbe (1988 - 1 Mark) (1985-1 Marky 2 2. 2B. 24. 28, 26. 2. (@)_ unionised in the small intestine and inthe stomach (6) completely ionised in the small intestine and in the stomach (©) ionised in the stomach and almost unionised in the small intestine (d)_ionised in the small intestine and almost unionised in the stomach Which one ofthe following isthe strongest acid? (1989 - 1 Mark) @ Cloyor () Co, (©) SOOH), (@) SOsOH), Amongst the following hydroxides, the one which has the lowest value of K,, at ordinary temperature (about 25°C) is (1990-1 Mark) @) Mg(OH, () CxOH, (©) BAON, @ BaOH, ‘The reaction which proceeds inthe forward direction is (1991-1 Mark (@)_ Fe,0,+6HCI- 2FeC,+3H,0 (b)_NH,+H,0+NaCl-> NH,C1+N2OH (©) SaCl,+Hg,Cl, > SnCl, +2HeCl, (@) 2Cul+1,+4K* 9 200+ 4KI The following equilibrium in established when hydrogen chloride is dissolved in acetic acid HC1+ CH,COOH = Cr+ CH,CooH} ‘The set that characterises the conjugate acid-base pairs is (1992-1 Mark) @) (HCL.CH,COOH) and(CH;COOH} ,cr) (b) (HCL, CH;COOH} )and(CH,COOH, Cr) (© (CH,COOH} , HCH and (Cr, CH,COOH) (@ (HCI,.Cr)and(CHjCOOH} ,CH,COOH) Which ofthe following solutions will have pH close to 1.0 (1992-1 Mark) 100ml of(M/10)HCL+ 100 ml of M/10) NaOH (6) SSmlof(M/10) HCI +45 ml of (M/10) NaOH. (©) 10mlof(M/10) HCI+ 90 ml of (W/10) NaOH (@ 75 lof MIS) HCI +25 ml of M/S) NaOH The degree of dissociation of water at 25°C is 1.9 « 10-7% and density is 1.0 gem-®. The ionic constant for water is (19955) @ 10x10? () 10x10 (© 10x10 @ 10*10% Which one is more acidic in aqueous solution. (1995S) @ Nia, (b) FeCl, (©) AIC, (@ Becl, The following acids have been arranged in the order of decreasing acid strength, Identify the correc order. CION(, BrOHAH, ION) —— (1996-1 Marky @ IPM () >I (© m>u>1 @ buenEquilibrium §——________ 29, 30, 31. 32. 33. o 35. The pl of 0.1 M solution ofthe following salts increases in the order. (1999-2 Marks) (@)_NaCI 2NO,(@) ‘Ata fixed temperature, the volume of the reaction container ishalved. For thischange, which ofthe following statements holds tre regarding the equilibrium constant (K,) and degree of dissociation (a)? (@) neither K, nor a changes (6) both K, and exchange (©) K, changes, but a does not change (@)_K, does not change, but a changes ‘A weak acid HX has the dissociation constant 1 < 10° M. Tt forms a salt NaX on reaction with alkali, The percentage a. hydrolysis of 0.1 M solution of NaX is (20045) (@) 0.001% ) 001% (©) 01% (@) 018% 4.0004 M solution of Na,SO, is isotonic with 0.010 M solution of glucose at same temperature. The percentage dissociation of Na,SO, is (20045) (@) 25% (&) 50% (©) 75% (@ &% 39. 0.1 mole of CH,NH, (K,= 5x10 *)ismixed with 0.08mole of HCI and diluted to one litre, What will be the HY concentration in the solution? 20055) (@) 8% 102M (b) 8x10™M © 16x10" (@) 8x 10M The Haber’s process forthe formation of NH, at 298K is Np +3Hy <=> 2NHy; AH = 460 KJ; Which of the following isthe correct statement (2006 - 3M, -) (@)_ Thecondition for equilibrium is Gy, +36n, ‘where G is Gibbis fee energy per mole ofthe gaseous species measured at that partial pressure ‘On adding N,, the equilibrium will shift 0 forward direction because according to 11% law of thermodynamics the entropy must inerease in the direction of spontaneous reaction (©) Theeatalyt will increase the rate of forward reaction by 2times and that of backward reaction by 1.5 times (None of these 2.5 ml of 2/5) M weak monoacidic base (Ky = 1 102 at 25°) is titrated (2/15) M HCI in water at 25°C. The concentration of Hat equivalence point is(K,= 1» 10-4 at25°C) 20085) @ 3710" () 32«107M (© 32*102M (@) 27*10?M Solubility product constant (K,,) of salts of types MX, (MX, and M,X at temperature ae 4.0 « 10°8, 32x 10-4 & 2.7% 1075, respectively. Solubiltes (mol dm) ofthe salts attemperature'T’are in the order (2008s) (@) MX>MX,>M,X —(b) M,X>MX,>MX (©) MX,>M,X>MX —(@), MX>M,X>MX, 40. Grins © a 2ory D EES For the gas phase reaction (1984-1 Mark) CyH,+ Hy = CoH, (AH -32.7keal) cariedoutin a vessel, the equilibrium concentration of C, can be inereased by (@)_ increasing the temperature (©) decreasing the pressure (©) removing some Hl (@)_ adding some C,H, ‘When NaNO, isheated ina closed vessel, oxygen islberated and NaNO, isle behind. Atequilibrium. (1986-1 Mark) (@)_ addition of NaNO, favours reverse reaction (6) addition of NaNO, favours forward reaction (©) increasing temperature favours forward reaction (@) increasing pressure favours reverse reaction Theequilibrium (1989-1 Mark) $0,C1,(@) = $0,(@)+ CL) {s attained at 25°C in a closed container and an inert gas, helium i introduced, Which ofthe following statements are correct? {@) Concentration of €0,, Cl; and $0,C1, donot change (b) More chlorine is formed (©) Concentration of $0, is reduced (4) More $O,CI, is formed For the reaction PCL(g) > PCI (g)+C1,(@) The forward reaction at constant temperature is favoured by @ ©) © (1991-1 Mark) introducing an inert gas at constant volume introducing chlorine gas at constant volume introducing an inert gas at constant pressure (@ increasing the volume of the container (6) introducing PCI, at constant volume For te reaction CO(g) + H,0(g) —=CO,(e) + Hg) ata given temperature the equilibrium amount of CO,(@) can be increased by (1998-2 Marks) (@) adding a suitable catalyst (6) adding an inert gas (6) decreasing the volume of the container (@_increasing the amount of CO(). Which ofthe following statements(s) is are) correct? (1998-2 Marks) ‘The pH of 1.0» 10-¥M solution of HCL is 8 “The conjugate base of HPO] is HPO} Autoprotolysis constant of water increases with temperature When a solution ofa weak monoprotic ai istirated against a strong base, at half neutralisation point pH=(12)pK, Aber solution cin be prepared from a mixture of (1999-3 Marks) sodium acctate and acctic aid in water sodium acetate and hydrochloric acid in water ammonia and ammenium chloride in water ‘ammoniaand sodium hydroxide in water @ ©) © @ @ o © @ __ Topiie-wise Sotved Papers - CHEMISTRY 8 Aqueous solutions of HNO,, KOH, CH,COOH and CH,COONs of identical concentrations ae provided. The pair(s of solutions which forma bulfer upon mixing is(ae) {@) HINO, and CH,COOHL (2010) (b) KOttandCHH,COONa (©) HINO, and CH,COONa (4) CH,COOHand CH,COONa 9. The initial rate of hydrolysis of methyl acetate (IM) by a ‘weak acd (IA, IM) is 1/100" ofthat ofa strong acid (HX, 1M), 25°C. The K, of HA is (GEE Ad: 2013) @ 1104 @) 1x10 © 1x10% @ 1103 10, TheKy of AgsCrO, is 1.1 «10-1? at 298 K. The solubility (inmol/L) of Ag,CrO, in a0.1 MAgNO, solution is (EE Ads. 2013) @ Lac! @) Lixiw (Lixo? @ Lixo 11, Thethermal dissociation equilibrium of CO.) is studied under different conditions (EL Adv. 2013) CaCO8) =¥ CaOKS)+CO,(2). For this equiibcium, the correct statement() sare) (@) Allis dependent on T (6). Kisindependent ofthe inital amount of CaCO, (©) Kis dependent on the pressure of CO, ata given T (@)_Atfisindependent of catalyst, ifany 12, The%yield ofammonia asa function of ime inthe reaction N4(@)+ 3H,(@) =» 2NH(2), AH Ty, he Dold oammenin aa Bn tine repel iy (abe ads 009) © © @ 5 Qf A solution contains Na,CO, and NaHCO, 10 ml of solution requires 2.5 ml of 0.1 MI1,SO, for neutralisation using phenolphthalein as an indicator. Methyl orange is then added when a further 2.5ml of 0.2M H,SO, was required Calculate the amount of Na,CO, and NaHCO, in one litre of the solution, (1979)Equilibrium §——________ ar 2 How many moles of sodium propionate should be added to ‘one litre of an aqueous solution containing 0.020 mole of propionic acid to obtain a buffer solution of pH 4.75? What will be pHif0.010 mole of hydrogen chloride i dissolved in the above buffer solution. Compare the last pH value with the pH of 0,010 molar HCI solution, Dissociation constant ofppropionic acid, K,at 25°C = 1.34 « 10-5 (1981-4 Marks) (One mole of nitrogen is mixed with three moles ofhydrogen ina4 litre container. 10.25 per cent of nitrogen is converted toammonia by the following reaction (1987-4 Marks) N,(@) + 3H,(g) = 2NH@), calculate the equilibrium constant (K,) in concentration units, What will be the value of K, for the following, equilibeium ? 1 3 Na) + 5 Ha) = Noa) Twenty ml of0.2 M sodium hydroxide is added to 50 ml. of 0.2 Macetic acid to give 70 ml of the solution. What is the pH ofthis solution? Calculate the additional volume of 0.2 MNaOH required to make the pH ofthe solution 4.74. The ‘nization constant of acetic acid is 1.8» 10-3 (1982-3 Marks) The dissociation constant ofa weak acid HHA is 49 = 10° ‘Afler making the necessary approximations, calculate (i) percentage ionization, (i) pH andi) OF concentration in adecimolar solution of the acid. Water has apH of 7. (1983 -2 Marks) ‘A solution contains a mixture of Ag (0.10 M) and Hg,"* (0.10M) which are tobe separated by selective precipitation Calculate the maximum concentration ofiodide ion at which cone of them gets precipitated almost completely. What percentage ofthat meta in is precipitated? [Kp Agl=85 « 10-17, Hel, =2.5 « 104] (1984-4 Marks) One mole of I, and 3 moles of PCL, are placed in a 100 litre vessel heated {0 227°C. The equilibrium pressure is 2.05 atmosphere. Assuming ideal behaviour, calculate the degree of dissociation for PCI, and K, forthe reaction PCL(g) =P PCL(e)+ CS) (1984-6 Marks) Arrange the following in (increasing bond length F>, N;, Cl Oy (1985 - 1 Mark) (1) increasing acid strength :HCIO,, HCIO,, HCIO,, HCIO (1986-7 Mark) (it) increasing basicity: H,0, OH, CH,OH, CH,O- (1921 Mark) (iv) Arrange the following oxides in the decreasing order ‘of Bronsted basicity Ba0, $0;,CO,,Cl,0,,B,0, (2004-2 Marks) ‘The [H] in 0.2 M solution of formic acid is 6.4 = 10° mole Titre". To this solution sodium formate is added so as 10 adjust the concentration of sodium formate to one mole litre“. What wil be pHT of this solution? K, for HCOOH is 2.4 x 10 and degree of dissociation of HCOONA is 0.75 (1985 -3 Marks) The equilibrium constant ofthe reaction A,(@) + B,(@) = 2AB(Q) M 18. Ww. 18, 19. 20. at 100°C sO. If one lie faskcotaning one mole ats connected ta two litte ask containing two mole of By how many mole ofAB wil be fomed at 373°C? (1985 - 4 Marks) ‘The solubility of Mg(OH) in pure water is9.57%10- glite, Calculate its solubility (in glitre) in 0.02 M Mg(NO,), solution, (1986 -$ Marks) ‘What ste pH¥ofthe solution when 0.20 moe ofhydrochloic acidis added to one litre ofa solution containing (1987 5 Mark) () 1 Meach of acetic acid and acetate ion? (i), 0.1 Meach of acetic acid and acetate ion? Assume the total volume i one lire. K, for acetic acid = 1.8 « 10-5 Ata certain temperature equilibrium constant K,) is 16 for thereaction (19875 Marks) $0,(g)+ NOJ@) = S08) + NO) Itwe take one mole each ofall the four gases in a ne litte container, what weuld be the equilibrium concentrations of NO(e) andNO{G)? NO, is 25% dissociated at 37°C and one atmosphere pressure Calculate (i) , and (i the percentage dissociation 210.1 atmosphere and 3! (1988-4 Marks) Howmany gram-mele of HCl wil be required to prepare one line of buffer solution eontaining NaCN and HC) of p18 using 0.01 gram formula weight of NaCN? Kdisocistion (HCN)=41 = 10" (1988-4 Mark) The equilibrium constant, ofthe reaction 280,(9)+ 0,(a) = 2808) is 900 am, a 8001 Amintre containing SO, and O having ini partial pressure of | and2 am. respectively isheated at constant volume to equilibrate Calulate the partial pressure of each gas at 800 K (1989-3 Marks) Freshly prespitated aluminium and magnesium hydroxides are stired vigorously in a buffer solution containing 0:25 mole! of ammonium chloride and 0.05 mole! of ammonium hydroxide. Calculate the concentration of aluminium and magresium ins insoluton: (7989-3 Mark) K,INHO1H]= 180° 10 KE IMe(OH),]=6 «10 Sp (AVOH,) =6 «10° Feorthe reaction” CO(g) +2H,(s) = CH,OH() hydrogen gas is introduced intoa ive lite Mask a 327°C, containing 0.2 mole of CO(g) and a catalyst, until the pressure is 4.92 atm. Atthis point 0.1 mole of CH, OH(g) is formed Calculate the equilibrium constant, K, and K. (1990 - § Marks) What isthe pl of 1.0 M solution of acetic acid? To what volume must one ltr ofthis solution be diluted sotha he pHloftheresuling solution wl be tvice the orginal value? Given: Ky= 1.810 (1990-4 Marks) “The solubility product of Ag,C,O, at 25°C is 1.29 « 10-7 ‘mol? A solution of KC,0, containing 0.1520 mole in 500 inl water is shaken at 25°C with excess of Ag,CO, til the followingequltrium isreached: (1997-4 Mark) ‘AB,CO, + K,C,0, = AgiC,0, +K,CO, Atequlibium the solution contains 00358 mole of K,CO, ‘Assuming the degree of dissociation of K,C,0, and K,CO, tobe equa, calculate the solubility prodact of Ag,CO,rd a 2. 2B 24. 26. n. 28, 29, 30. __ Topiie-wise Sotved Papers - CHEMISTRY ‘A.40.0 ml solution of weak base, BOH is titrated with 0.1N HEI solution, The pH of the solution is found to be 10.08 and 9.14 after adding 5.0 ml and 20.0 ml of the acid respectively Find out the dissociation constant ofthe base (1991 - 6 Marks) The solubility product (K,,) of Ca(OH), at 25°C is 4.42 * 10-5, A500 mi, of saturated solution of Ca(OH, is mixed with equal volume of 4 MINaOH. How much Ca(OH), inmilligramsis precipitated? (1992-4 Marks) 0.1S mole of CO taken in a2 flask is maintained at 750K along with a catalyst sothat the following reaction can take place CO(g) + 2H2(g) <> CHsOH() Hydrogen is introduced until the total pressure ofthe system {s 8.5 atmosphere at equilibrium and 0.08 mole of methanol is formed, Calculate (i) K, and K.and i) the final pressure if the same amount of CO and H, as before are used, but with no catalyst so that the reaction does not take place. (1993-5 Marks) The pH of blood stream is maintained by a proper balance of HCO, and NaHCO, concentrations. What volume of SMNaHHCO, solution should be mixed witha 10 ml sample ofblood which is2M in HCO, in order to maintain a pH of 7.4K, for HCO, in blood is 78 = 10-7, (1993-2 Marks) ‘An aqueous solution of a metal bromide MBr, (0.05M) is saturated with HS, What is the minimum pH1at which MS will precipitate? (1993-3 Marks) Kp for MS=6.0x10!, concentration of saturated H)S=01M K,=107 and Ky =1.3%10, for Hs Attemperature 7, compound AB, (g dissociates acording tothe reaction (1994-4 Marks) 2AB3(¢) <== 2AB(g) +B3(e) with a degree ofissociation x which issmall compared with nity. Deduoe the expression forx in terms ofthe equilibrium constant K, and the total pressure, P For the eaetion IAS(CN) 27 <== Ag’ +2N~ the equilibrium constant at 25°C is 4 010°! Caleulate the silver ion concentration ina solution which was originally 010 molar in KCN and0.03 molar in AgNO), (1994-3 Marks) Caleuate the pH ofan aqueous solution of 1.0 Mamamonium formate assuming complete dissociation (pK offormic acid=3 8 and pK, ofammonia=4:8.) (1995-2 Marks) ‘Whats the pl¥ofa0 50 M aqueous NaCN solution? pK, of CN-i84.70, (1996-2 Marks) A sample of AgCI was treated with 5.00 mL of 1.5 M Na,CO, solution togive Ag,CO,, The remaining solution contained 0.0026 g of CI per litre. Calculate the slubili product of AgCI (K,,(Ag,CO,)=82 * 10°) (1997-5 Marks) 31. An acid type indicator, Hin differs in colour from its conjugate base (In-). The human eye is sensitive to colour differences only when the ratiofin-V/[HIn] is greater than 10 cor smaller than 0.1. What shouldbe the minimum change in the pH ofthe solution to observe a complete colour change (K=Lo-1052 (1997-2 Marks) Given: Ag(NH,) 3 —=Ag*+2NH,,K,=62% 10S and K of AgCI= 1.8 » 10"! at298 K, Ifammonia isadded to2 vwilter solution containing excess of AgCI(s) only, calculate the concentration ofthe complexin 1.0 M aqueous ammenia. (1998-5 Marks) ‘What will be the resultant pH when 200mL of an aqueous solution of Cl (pH1=2.0) ismixed with 300 ml. of n aqueous solution of NaOH (pH1= 12.0)? (1998 - 2 Marks) 34, When 3.06 g of solid NHHS is introduced into a two litre evacuated flask at 27°C, 30% of the solid decomposes into gaseous ammonia and hydrogen sulphide. (i) Calculate K, and K, forthe reaction at 27°C. (ji) What would happen to the equilibrium when more solid NH,HS is introduced into the flask ? (1999-7 Marks) 38. Thesolubility of POH) in water is 6.7>10-°M. Calculate the solubility of POH), ina buffer solution of plt=8, (1999-4 Marks) 36. ‘Theaverage concentration of SO, inthe atmosphere overa city on a certain day is 10 ppm, when the average temperature {298 K. Given that the solubility of, in water at 298 K is 1.3653 moles ltr and the pK, of H,SO, is 1.92, estimate the pH ofrain on that day (2000-5 Marks) 37. 500 mL of 0.2.M aqueous solution of acetic acid is mixed with $00 mL of0.2 MHC at 25°C. (Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the solution. (If 6 g of NaOH is added to the above solution, ‘determine the final pH. [Assume there sno change in volume on mixing; K,,ofaceticacid is 1.75 » 10 mol]. (2002-5 Marks) 38, Match the following ifthe molecular weights of X, Yand Z aresame. (2003-2 Marks) 32. 3. PARAGRAPH ‘When 100 mL of .0M HCl was mixed with 100 ml. of 1.0 MNaOHT inan insulated beaker at constant pressure, a temperature increase ‘of 5.7 °C was measured for the beaker and its contents (Expt. 1. Because the enthalpy of neutralization of a strong acid with a strong base is constant (-57.0 kJ mol"), this experiment could be used to measure the calorimeter constant. In a second experiment Expt 2), 100 mL of 2.0 M acetic acid (K,=2.0* 10-5) ‘was mixed with 100 mL of 1.0 M NaOH (under identical conditions toExpt. 1) wherea temperature rise of 56 °C was measured (Consider heat capacity of all solutions as 42 J g-! K-! and density ofall solutions as 1.0 g mL!) GEE Ads. 2015)Equilibrium §——________ a7 1. Enthalpy of dissociation (in kJ mol"! of acetic acid obtained from the Expt2is @ 10) 100 (@ 25 2 ‘ThepHfof the solution after Expt. 2s @ sia (@) 28 () 47 © 50 @ 70 PARAGRAPH? ‘Thermal decomposition of gaseous X, to gaseous X at 298 K takes place according tothe following equation: X2(g) = 2X(g) ‘The standard reaction Gibbs energy, A,G°, of this reaction is positive. At the start ofthe reaction, there is one mole of X, and ‘no X. As the reaction proceeds, the numberof moles of X formed is given by B. Thus, Baga the number of moles of X formed at equilibrium, The reaction is carried out at a constant total pressure of 2 bar. Consider the gases to behave ideally (Given R=0,083 L bar K-! mot") (EE Adv: 2016) 3. The equilibrium constant K, for this reaction at 298 K, in terms Of Beas iS shdttoun Sita o> © Ee ait i $Péqutvin PG qatium © TF. © Oe atc dean 4. The INCORRECT statement among the following, for this reaction, is (@) Decrease inthe total pressure will result in formation ‘of more moles of gaseous X (©) At the start of the reaction, dissociation of gaseous X, takes place spontaneously (©) Bagattvim = 0.7 @ Keel 5 EG 1, Each question contains STATEMENT (Assertion) and STATEMENT-2 (Reason). Each question has5 choices (a), (b), (€) and (4) out of which ONLY ONE is correct. Ma your answer as, (@) If both Statement -1 and Statement -2 are correct, ‘and Statement -2 is the correct explanation of the Statement-2 I Section-B te 44 1. MINaCl and 1 MCL are present in an aqueous solution “The solution is. 12002] (@) nota buffer solution with pH<7 (b)_ not a buffer solution with pH> 7 (©) buffer solution with pH<7 (@)_ buffer solution with pH>7. 2 Species acting as both Bronsted acid and base is (b) Ifboth Statement -1 and Statement -2 are correct, but Statement -2 is not the correct explanation of the Statement 1 (©) 1fStatement-1 is correct but Statement-2 is incorrect (@)_1fStatement-l is incorrect but Statement-2 iscorrect Statement -1 The endothermic reactions are favoured at Tower temperature and the exothermic reactions are favoured at higher temperature. Statement-2 When a system in equilibrium is disturbed by changing the temperature, it will tnd to adjust itself so as foovercome the effect of change. (1991-2 Marks) Read the following statement and explanation and answer as per the options given below Statement 1 HNO, isa stronger acid than HINO, Statement -2 In HINO, there are two nitrogen-to-oxygen bbonds whereas in HNO, there is only one (1998 -2 Marks) Statement -1 For every chemical reaction at equilibrium, standard Gibbs energy of reaction is zero, ‘Statement-2 At constant temperature and pressure, chemical reactions are spontaneous in the direction of decreasing ibbs energy, (2008) 1 Eee 0.1 MNaOH is titrated with 0.1 M HA till the end point; K, for HA is 56 « 10-°and degree ofhydolysisis ess compared to 1. Caleulate pH ofthe resulting solution atthe end point (2004-2 Marks) The dissociation constant ofa substituted benzoic acid at 25°Ciis 1.0 * 10+ ThepH1 of 0.01 Msolution ofits sodium saltis (2009-2 Marks) ‘Amongst the following, the total number of compounds ‘whose aqueous solution turns red litmus paper blue is KEN, K,S0,,(NH,),C,0,,NaCl, Zn(NO,),, FeCl, K,CO,, NHNO, and LiCN 2010) The total numberof diproti acids among the following is: HPO,, H,SO,, H,PO,, H,CO,, H8,0,, HyBO,, H,PO,, H,C10, and 1,80, 2010) In | Lsaturated solution of AgC! [Kw(AgCl)= 1.6% 1079}, 0.1 mol of CuCl [K,(CuCl) = 1.0 x 10-4] is added. The resultant concentration of Ain the solution is 1.6 x 10" The value of "is, en @ (soy! (b) Na,CO, 2002] (©) NH @ on Let the solubility ofan aqueous solution of Mg(OH), be x then its K,, is 2002] @ 4 () 1088 (@ 2 (a) % Change in volume ofthe system does not alter which ofthe following equilibria? (2002)ory (@)_Ny(@)+0,(@) === 2N0(@) (b) PCIs(g) ==> PCI; (2) +Cl, (2) (©) N,(2)+3H, @) ——=2NH (8) @ $0,C1,(2) ——=* 80, (g) +Cl, (@). For the reaction (g) + (1/2) 0, ()= CO (g), Ky/ Kis @ ar () (ery! {2002} (orn? (@) (Rn! Which one of the following statements is not true? [2003] (a) pH+pOH= 14 for all aqueous solutions (b) ThepH of | x 108 MHCIis8 (©) 96,500 coulombs of electricity when passed through a ‘CuSO, solution deposits 1 gram equivalent of copper atthe cathode (@ Theconjugate base of HPO; is HPO} The solubility in water of a sparingly soluble salt AB is 1.0 10-$ mol L-"_ Its solubility product number will be @ 4x10 (by 1x10 12003), © 1x10” (@ 4x10 Forthe reaction equilibrium [2003], 1N,0, (@)==2 NO, (2) the concentrations of N,O, and NO, at equilibrium are 4.8 «10 and 1,2 « 10 mol L“ respectively. The value of K, forthe reaction is (@) 3x10! mal (b) 310% mal L-* (© 3*10'maL* (@) 33% 10%molL“ Consider the reaction equilibrium 280, (g) + Og) = 2 $0, (g); AH?=-198kI On the basis of Le Chatelier’s principle, the condition favourable forthe forward reaction is (@) increasing temperature as well as pressure (b) lowering the temperature and increasing the pressure (©) any value of temperature and pressure (@)_ lowering of temperature as wel as pressure ‘When rain is accompanied bya thunderstorm, the collected rain water will have a pH value (2003) (@) slightly higher than that when the thunderstorm isnot there (b)_uninfluenced by occurrence of thunderstorm (©) which depends on the amount of dustin air (@) slightly lower than that of rain water without [2003] thunderstorm, The conjugate base of HPO, is [2004 (@) HPO, (b) P05 (© Poy @ HPO} What is the equilibrium expression for the reaction P,(s) +50 (2) => PyO;0(8)? 2004] @ K,=[0,) (6) K.=[P,O40)/51P, 102] © Ke= [Op VPsOrP @ K.=102)° 1B. 16. a 19 Topic-wise Solved Papers - CHEMISTRY For the reaction, CO(g)+Cla(g) = COCI,(e) the "Vf, iscqulto (2005) @ JRF © Rr © Mer @ 10 The equilibrium constant for the reaction Na(g)+02(g) = 2NO2(g) at temperatures 4104 The value ofK, fr the reaction NOz(@) => 4N2(o) + L0;(@ atthesame temperature is @ 4x10+ 0» [20041 () 25x18 @ 00 The molar solubility (in mol L~') ofa sparingly soluble salt MX, is*s’. The corresponding solubility product is K,,,°s” is given interm of K,, by the relation 2004) @) 5=Q256Ky)"> (b)s= (128K) (©) 8= (Ky /128)""* (d)s = (Ky /256)"> If ais the degree of dissociation of NaqSO, the Vant Hoff’s factor (i) used for calculating the molecular mass is (2005) @ 1-20 ©) 12@ (©) l-a @) Ita The solubility product of a salt having general formula MX. in water is: 4 10", The concentration of M?* ions in the aqueous solution ofthe salts 120051 (@) 40x10 M (b) 16x104M © 10%10M @ 20%10-°M The exothermic formation of CIF, is represented by the equation h(a) + 3%(@) 2201 @) ; AH =—3291 Which ofthe following will inerease the quantity of CIF; in an equilibrium mixtureof Clz, F; and CIF,? [2008] (@) Adding F (b) Increasing the volume of the container (©) Removing Cl, (@)_ Increasing the temperature For the reaction : 2NOs) == 2NO{s) + O21 (K, =1.8% 10" at 184°C) (R=00831 kd/(mol.K))Equilibrium 20, 2 2. 2B. 24, 25, When K,, and K are compared at 184°C, itis found that 2005) (@) Whether K,, is greater than, less than or equal to K,, depends upon the total gas pressure (©) K, isless than K, ()_K, isgreater than K, Hydrogen ion concentration in moVL in solution of pH=S4 willbe 12005), (@ 3.98«10% (&) 3.6810 (© 388x108 (@ 398x108 ‘What isthe conjugate base of OH ? 2003} 28. @ oF ©) oO © 1,0 @ o ‘An amount of solid NHgHS is placed in a flask already containing ammonia gas ata certain temperature and 0.50 atm pressure. Ammonium hydrogen sulphide decomposes to yield NH and HS gases in the flask. When the decomposition reaction reaches equilibrium, the total pressure in the flask rises to 0.84 atm? Te equilibrium constant for NHyHS decomposition at this temperature is @ on ) 017 {2005}, (©) 018 @ 030 Phosphorus pentachloride dissociates as fellows, ina closed reaction vessel 12006), PCL(g) > PCL@)+CL@) total pressure at equilibrium ofthe reaction mixture is P and degree of dissociation of PCI, is x, the partial pressure of PCI, willbe o (a or or 29. 1 $0,(8) => 802(¢)+ 50218) isk, 9 « 10. The value of K for the reaction 280,j@)+ 0(e) => 280,@) willbe @) 98x10? © 416 Given the data at25°C Ag+I” —> Agl +e” 12006) (b) 49107 (©) 240% 103 2 E°=0,152V Ag—+Ag*+e” — E°=-0800V oD Whatisthe value oflog Kor Al? (2.303 RTF=0.059V) @ 3783 () 1613 12006) @ 82 (@ 1862 ‘The first and second dissociation constants of an acid H1,A are 1.0» 10°S and $.0 10"! respectively. The overall disso- ciation constant of the acid will be 12007] (@) 02% 108 (b) 50x 10-5 (© 50x10! (@ 50x10 ‘The pK, ofa weak acid (HHA) is 4.5. The pOH of an aqueous butler solution of HA in which S0% of the acid is ionized is @ 70 (b) 45 12007] © 25 @ 95 Ina saturated solution ofthe sparingly soluble strong clec- trolyte AgIO, (molecular mass=283) the equilibrium which setsin is AgIO, AB ag) #1054) the solubil- ity product constant K, of AIO, at given temperature is 1.0 « 10-4, what isthe mass of AgIO, contained in 100 ml of its saturated saolution? 12007] (@) 10«104g (b) 283x102¢ (o) 283% 103g d) 10* 107g. ‘The equilibrium constants K,, and Kp for the reactions X=2Yand Z = P +Q, respectively are in the ratio of 1 9. Ifthe degree of dissociation of X and Z be equal then the ratio of total pressures at these equilibriais [2008] (@ 1:36 Ome © 13 @ 19 For the following three reactions a, b and c, equilibrium constants are given: {2008} (COL) + H0(@) = CO2(2) +119(8):Ky (CHC) +H,0() = COKE) +3H3(@).K (i)CHHy(@) +2018) CO, (@)+ 4H (@):Ky @) Ki Rr = Ks () KaKy= Ky (©) Ky=K\K, Four species are listed below: 12008) i HCOS i, H0* ji WSO, iw HOF Which one ofthe following isthe correct sequence oftheir acid strength? @ iv1,0"+H,Po,- (i) HPO, +H,0-> HPO2-+H,0" Gi) H,PO,-+ OH > H,PO,+0™ In which ofthe above does HPO} act asan acid ? [2010] @) Gionly (©) @and(ii) (© Giiyonly © (only 35. In aqueous solution the ionization constants for carbonic acidare K,=42% 107 and K,=4.8 «101 Select the correct statement fora saturated 0.034 M solution ofthe carbonic acid P2010), (@)_ The concentration of COR” is0.034 M. (6) The concentration of CO3- is greater than that of HCO} (©) The concentrations of H* and HCO; are approximately equal, (@ The concentration of H* is double that of CO}- 36. Solubility product of silver bromide is $0 = 10°! The quantity of potassium bromide (molar mass taken as 120 g mot) to be added to | lite of 0.05 M solution of silver nitrate to start the precipitation of AgBr is 2010) @ 12x10 () 12108 © 62x 105g (@ 50x10%g 37, At2S°C, the solubility product of Ma(OH), is 1.0 * 10-1. At ‘hich pi, wll Mg?* ions stat precipitating inthe form of Me(OH), from a solution of 0.001 MMg2*ions? [2010] @ 9 &) 10 ou @ 8 38. A vessel at 1000 K contains CO, with a pressure of 0.5 atm. Some ofthe CO, is converted into CO on the addition of graphite. Ifthe total pressure at equilibrium is 0.8 atm, the value of Kis Pont] @ 18am () 3aum (© 03am (@) 018i 39. The equilibrium constant (K,) for the reaction N,(@)+0,(g) > 2NO(g) at temperature Tis 4« 10-4 The value of K, forthe reaction por} NO{e)-» £No(e)+4.02(8) atthe same temperatures (@ om © 4x104 &) 25% 10 @ 00 40. aL 2. 45. _ Tropiie-wise Solved Papers «CHEMISTRY ‘The pH of 0.1 molar solution ofthe acid HQis 3. The value ofthe ionization constant, K, ofthe acidis (2012) @ 3x101 () 1103 (1105 @ 1107 How many litres of water must be added to 1 Titre an aque- ‘us solution of HCI with a pH of I to ereate an aqueous, solution with pH of 2? [EE M2013} (@ ol, (b) 09L (©) 201, (@ 90L Lom For the reaction SO,j9)+503(g)—S0y,), if Kp =Ke(RT)" where the symbols have usual meaning then the value of is (assuming ideality) 1 [DEE M2014), @ = © 1 © ‘The standard Gibbs energy change at 300 K for the reaction @ 1 2A == B+Cis2494.21. Ata given time, the composition etterocionniauctA]=+,]-2aC}=4 ne reaction proceeds inthe: [R=8 314 J/K/mol, e=2.718] [SEE M2015] (@) forward direction because Q K, (@) reverse direction because Q> K, ‘The following reaction is performed at 298 K. 2NO{g)+ 0,(g) == 2NO,() ‘The standard ffer energy of formation of NO{g) is 86.6 kjimol at 298 K, What is the standard free energy of formation of | [NO4(g) at 298 K?(K, = 1.6 10!2) [JEE M2015] In (1.610) R98) (b)_0.5[2 « 86,600-R(298) In(1.6 = 10") (©) R298) In(1.6> 1012)-86600 (€)86600+R(298) n(1.6 10) ‘The equilibrium constant at 298 K for areaction A +B ‘C+Dis 100. Ifthe initial concentration ofall the four species ‘were 1 Meach, then equilibrium concentration of D (in mol (2) 86600— L)will be [SEE M2016), (a) 1818 Le (©) 01g @ 818CHAPTER The s-Block Elements I Section-A B)4aGIVCIS alip 43 FA Fillin the Blanks Anhydrous MgCl, is obtained by heating hydrated salt with (1980) 2. The absorption of hydrogen by palladium is commonly known as (1983-1 Mark) 3. Sodium dissolved in liquid ammonia conducts electricity because (1985-1 Mark) 4. Theclectrolyss of molten sodium hydride liberates gasatthe (1989-1 Mark) Ca?* has asmaller ionic radius than K” because thas (2993-1 Mark) 8 Ri MgCl, 6H0 on heating give anhydrous MeCl (1982 - 1 Mark) 2, Thesofiness of group I-A metals increases down the group with increasing atomic number. (1986-1 Mark) 3. Sodium when burt in excess of oxygen gives sodium oxide. (1987-1 Mark) c PRC A substance absorbs CO, and voilently reacts with water. The substance is a) (@ Caco; &) CO (©) 180, @ 70 2. HCLis added to following oxides. Which one would give H,0,? 198) (@) MnO, (b) PbO, (©) B20, 8140 (@ No, 3. Calcium isobtained by assy) (@) electrolysis of molten CaCl, (b) electrolysis of solution of CaCl in water (©) Reduction of CaCl, with carbon, (@)_ roasting of limestone ‘A solution of sodium metal in liquid ammonia is strongly reducing due to the presence of (1981-1 Mark) (@) sodium atoms (6) sodium hydride (©) sodium amide (@) solvated electrons Heavy water is (@ 1,0 (b) water obtained by repeated distillation © D,0 (@) water at arc ‘The hydration energy of Mg** is larger than that of (@ Ab (b) Nat (1984-1 Mark) (0) Bet* (@ Mg ‘The oxide that gives hydrogen peroxide on treatment with a (1983 - 1 Mark) dilate acid is (1985-1 Mark) @) PbO, (6) Ne,0, (©) MnO, (@ Ti, Molecular formula ofGlauber’ssaltis: (7985-1 Mark) (@) MgSO,.7H,0 (b) CuSO, SH,0 (©) FeSO, 7H,0 (@ Na,S0,,101,0 Hydrogen gas will not reduce (1985-1 Mark) (@) heatedcupric oxide (b)_ heated ferric oxide () heated stannic oxide (4) heated aluminium oxide The pair of compounds which cannot exist together in solution is (1986-1 Mark) (@) NaHCO, andNaOH — (b) Na,CO5 and NaliCO, (©) Na,CO,and NaOH (@)_NalICO, and NaCl Themetalliclustre exhibited by sodium is explained by (@) diffusion of sodium ions (1987-1 Mark) (6) ascillation of lose electrons (6) excitation of free protons (@) existence of body centered cubic lattice The volume strength of 15 N HO, solution is @ 48 (b) 84 (1991-1 Mark) © 30 @ 80 The following compounds have been arranged in order of their nereasing thermal stabilities. Identify the correct order. (1996-1 Mark) K,C0,() MgCO,(Il) CaCO, (Ill) BeCO, IV) @ INa>Li (b) Be>Mg>Ca (©) B>C>N (@) Ge>si>c GP_3021roy £3, A sodium salt on treatment with MgCl, gives white precipitate only on heating. The anion ofthe sodium salt is (@ HCo; ©) cod (20048) © Nox @ soy ‘Hydrogen peroxide in its reaction with KIO, and NH,OH respectively is acting as a (IEE Ads: 2014) (@) Reducing agent, oxidising agent (&) Reducing agent, reducing agent (©) Oxidising agent, oxidising agent (2) Oxidising agent, reducing agent D BRR ieeaoce 1. When zeolite, which ishydrated sodium aluminium silicate, is treated with hard water the sodium ions are exchanged 16. with (1990-1 Mark) @) Hons (6) Ca** ions (©) $0,-~ ions (@ Me™ ions (©) OFF ions 2. The species that do not contain peroxide ions are (1992-1 Mark) (@) PbO, (©) 1,0, (© S10, (@ B20, 3. Highly puredilute solution of sodium in liquid ammonia (@)_ shows blue colour (1998-2 Marks) (6) exhibits electrical conductivity (©) produces sodium amide (@_ produces hydrogen gas. 4. The species present in solution when CO, is dissolved in water are (2006 - 5M, —) @) CO,,H,C0,,HCO;-,CO,* (6) H,C0,,CO,* (©) CO,-,NCO- (@) €O,,1,CO, MgSO, on reaction with NH,OH and Na;HPO, forms @ ‘white crystalline precipitate. What isis formula? (2006 -5M,-1) (@) Mg(NH,)PO, (b) Mgs(PO4)2 (©) MgCl MgSO, (@) MgSO, 6. The compounds) formed upon combustion of sodium metal inexcess air is(are) @) Na,0, (0) NaO (2009-5, -) (© Na0, (@) NaOH 7. The reagent(s) used for softening the temporary hardness of ater is (are) 2010) @ Cas(PO,), (©) caor, (©)_Na,CO; (@)_Neocl E E@rnoins |. Givereasons forthe following (Sodium carbonate is made by Solvay process but the same process is not extended to the manufacture of | potassium carbonate (1981-1 Mark) 10. __ Topiic-wise Sotved Papers - CHEMISTRY (ii) Hydrogen peroxide is a better oxidising agent than water. (1986-1 Mark) (iit) Magnesium oxide is used forte lining of tee! making furnace. (1987-1 Mark) (¢»)_ Why is sodium chloride added during electrolysis of fused anhydrous magnesium chloride? (1987-1 Mark) (*) Hydrogen peroxide acts as an oxidising as well as a reducing agent. (1992-1 Mark) (%) The crystalline salts of alkaline earth metals contain ‘more water of crystallisation than the corresponding alkali metal salts (1997-2 Marks) (it) BeCl, can be easily hydrolysed. (1999-2 Marks) How will you prepare bleaching powder from slaked lime (1982-1 Mark) Write down the balanced equations fr the reactions when (9 Caleum phosphate is heated with a mixture ofsand and carbon; (1985-1 Mark) (i) An alkaline solution of potassium ferricyanide is reacted with hydrogen peroxide. (1982-1 Mark) (iit) Carbon dioxide is passed through a concentrated ‘aqueous solution of sodium chloride saturated with ‘ammonia. (1988-1 Mark) (iv) Potassium ferricyanide reacts with hydrogen peroxide inbasie solution (1989-1 Mark) (©) Carbon dioxide is passed through suspension ofime stone in water. (1991-1 Mark) Give briefly the isolation of magnesium from sea water by the Dow process, Give equations forthe steps involved (1993-3 Marks) Complete and balance the following reactions Cas(PO4)3F +1804 +1130 BSL + SCASOg 220 + (1994-1 Mark) 45.0 em solution of 1,0, liberates 0,508 g ofiodine from an acidified KI solution, Calculate the strength of HO, solution in terms of volume strength at STP. (1995 -2 Marks) Explain the difference in the nature of bonding in LiF and LiL (1996 - 2 Marks) To a 2Sml H,O, solution, excess of acidified solution of potassium iodide was added, The iodine liberated required 20 ml of 0.3 N sodium thiosulphate solution. Calculate the volume strength of H,O, solution. (1997- $ Marks) Givereactions forthe oxidation of hydrogen peroxide with potassium permanganate in acidic medium, (1997-1 Mark) Element 4 burns in nitrogen to give an ionic compound B. Compound B reacts with water to give Cand D. A solution ‘of C becomes ‘milky” on bubbling carbon dioxide. Identify A,B, Cand D. (1997 -3 Marks)‘The s-Block Elements ——____ 11, Arrange the following sulphates oalkaline earth metals in order of decreasing thermal stabil 04, MgSO, C480,,S150, (1997-1 Mark) 12, Work out the following using chemical equation: Chlorination of calcium hydroxide produces bleaching powder (1998 - 2 Marks) 13. Hydrogen peroxide acts both as an oxidising and as a reducing agent in alkaline solution towards certain first row transition metal ons. lustre both these properties of H,O, using chemical equations. (1998 - 4 Marks) BH RSet 1, Read the following statement and explanation and answer as per the options given below ‘Statement : Thealkali metals can form ionic hydrides which contain the hydride ion Hr. Explanation : The alkali metals have low electronegativity; their hydrides conduct electricity when fused and liberate hydrogen at the anode. (1994 -2 Marks) I Section-B 1. KO, (potassium super oxide) is used in oxygen cylinders in space and submarines because it 12002) (@) absorbs CO, and increases O, content (©). climinates moisture (©) absorbs CO, (produces ozone. 2. The metallic sodium disolves in liquid ammonia to form a deep blue coloured solution, The deep blue colour is de to formation of 12002] (@)_ solvated electron, e(NH3); (0) solvated atomic sodium, Na(NH), (©) (Na +N) (8) NaNH,+H, 3. Ametal M readily formsits sulphate MSO, which is water soluble, It forms its oxide MO which becomes inert on heating, It forms an insoluble hyroxide M(OH), which is soluble in NaOH solution. Then Mis 12002) @ Mg (®) Ba © (@) Be. 4. Incuring cement plasters water is sprinkled from time to time. This helps in 12003] (@) developing interlocking needle-like crystals ofhydrated silicates (b) hydrating sand and gravel mixed with cement (c) converting sand into silicic acid (@) keeping itcoot ana 5 53 (@) Both S and E are trueand Fis the correct explanation of. (6). Both Sand Earetrue but Eis not the correct explanation of. (© Sistruebut Eis file (@) Sisfalse but Eistrue This question contains STATEMENT:1 (Assertion) and STATEMENT-2 (Reason) and has 4 choiees (a, (D),(€) and (€) outof which ONLY ONE is correct. 2007) STATEMENT-1: Alkali metals dissolve liquid ammonia to give blue solutions. because STATEMENT? : Alkalimetalsis liquid ammonia give sol vated spevies of the type [M(NH,),]°(M= alkali metals. (@) Statement is True, Statement-2is True, Statement-2 ‘isa correct explanation for Statement-1 (©) Statement is True, Statement-2s True, tatement-2 isnot correct explanation for Statement-I (©) Statem (Statement is False, Statement-2is True Lis True, Statement-2is False The substance not likely to contain CaCO is (@) calcined gypsum (0). sea shel, (c) dolomite (d)_ amarble statue The solubilities ofearbonates derease down the magnesium sroup due toa decrease in 12003} (a) hydration energies of cations (b) inter-ionie attraction (c)_ entropy of solution formation (@) lattice energies of solids Which one of the following processes will produce hard water? [2003] (a) Saturation of water with MgCO,, (©) Saturation of water with CaSO, (©) Addition of Na,SO, to water (4) Saturation of water with CaCO, One mole of magnesium nitride onthe reaction with an excess of water gives {2004} (a) twomoles ofammonia (b) onemole of nitric acid (c) one mole ofammonia (@) womolesofnitricacid Which ofthe fllowing species is diamagnetic in nature? 12003] @ Hy HE (2005) © @ Heser) 0. UL 2, 1B. 18, 16. —_ Tropiie-wise Solved Papers «CHEMISTRY ‘sased on lattice energy and other considerations which one of the following alkali metal chlorides is expected to hhave the highest melting point ? [2005] @) RbCl () kal (©) Nea @ La Which of the following statements in relation to the hydrogen atom is correct ? (2005) (@) 3s, 3p and 3d orbitals all have the same energy (b) 3sand3p orbitals are of lower energy than 3d orbital (©). 3porbital is lower in energy than 3d orbital (@)_3sorbita islower in energy than 3p orbital The ionic mobility ofalkali metal ions in aqueous solution is ‘maximum foe [2006] @ Lit (b) Nat © K (@) Rb* Incontext with the industrial preparation ofhydrogen from ‘water gas (CO +H), which ofthe following isthe correct statement? 12008), (@) COand H,, are factionally separated using differences intheir densities (©) CO is removed by absorption in aqueous CuCl, solution (©) Hh isremoved through occlusion with pd (8) COs oxidised to CO, with steam in the presence ofa ‘catalyst followed by absorption of of CO, in alkali Which ofthe following on thermal decomposition yields a basic as well as acidic oxide? 12012} (@) NaNO, () KCO, (©) Caco, (@)_NH,NO; Very pure hydrogen (99,9) can be made by which ofthe following processes ? 012] (@) Reaction of methane with steam (b)_ Mixing natural hydrocarbons ofhigh molecular weight (©) Electrolysis of water (@) Reaction of sats ike hydrides wth water In which ofthe following reactions H,0, acts as a reducing agent? [JEE M2014] (@)Hy0, +2H* +2e" + 2,0 (0) H,0)+2e° +0, +24" ”. 18, 19 a. 2, (©) Hy0,+2e" +2087 (@ 11,0) +2017 ~2e" +03 +21,0 Which one of the following alkaline earth metal sulphates hasitshydration enthalpy greater than its lattice enthalpy ? [EE M2015), @) Baso, (©) S180, (©) Cas0, (©) BeSO, The molecular formula of a commercial resin used for exchanging ions in water softening isCgH,SO,” Na® (Mol ‘wt 206. What would be the maximum uptake of Ca? ions by the resin when expressed in mole per gram resin ? [JEE M 2015) 2 ay ® 509 © tp 1 1 © igs @ 206 From the following statements regarding H,02, choose the ‘incorrect statement IJEE M2015], (@) thas tobe stored in plastic or wax lined glass bottles indark (6) thas to be kept avay from dust (©) Iteanact only asan oxidizing agent (@_ It decomposes on exposure to light ‘Which one ofthe following statements about water is FALSE? [EE M2016), (@) There is extensive intramolecular hydrogen bonding in the condensed phase, (6) Ice formed by heavy water sinks in normal water. (©) Water is oxidized to oxygen during photosynthesis. (8) Water can act both as an acid and as a base ‘Which ofthe following atoms has the highest frst ionization energy? [JEE M2016), @ K () Se (©) Rb @ Na ‘Themain oxides formed on combustion of Li, Naand K in excess ofr are, respectively: [JEE M2016), (@)_Li,0,,Na,O, and KO, (b) Li,O,Na,0, and KO, (©) 1i,0,NaOand KO, ” (@) LiO,,Na;0, and Kj0CHAPTER Organic Chemistry — Some Basic Principles and Techniques | ccc JEE Advanced) IIT-EE FW Fillin the Blanks 1. Among the given cations, ismost stable. (1981) (sec-butyl carbonium ion; frt-butyl carbonium ion; n-butyl carbonium ion) 2. The compound having both sp and sp* hybridized carbon ators. «9s, (propene, propane, propadiene) 3. ring is most strained. (98) (Cyclopropane, Cyclobutane, Cyclopentane) 4. ‘Theterminal carbon atom in butane is haybriised. (1985) BOA diol has two hydroxyl groups on carbon atoms. (1986) 6. Isomers which are mirror images are known as (1988) (superimposable, non-superimposable, enantiomers, diastereomers, epimers) 7. Thevalence atomic orbitals on carbon in silver acetylide is hybridized, 4990) 8. Thekind of delocalization involving sigma bond orbitals is called (1994) The IUPAC name of succinic acid is (194) 5’ Rio 1. Iodide isa better nucleophile than bromide. (1985 - % Mark) 2, An electron donating substituent in benzene orients the incoming electrophilic group tothe meta position, (1987) 3. 2,3,4Trichloropentane has three asymmetric carbon atoms, (90) 4. During $1 reaction, the leaving group leaves the molecule before the incoming group is attached to the molecule (190) c BRC 1. The bond order of individual carbon-carbon bonds in benzene is (198i) (@)_ one (6) between one and two (&) two (@)_one and two, alternately 2 Molecule in which the distance between the two adjacent carbon atoms is largest is (1981) (@). Ethane (b) Ethene (©) Ethyne (@) Benzene ‘The compound which isnot isomeric with diethyl ether is (1981) (2) mpropyl methyl ether (6). butan-I-ol (©) 2-methyipropan-2-o1(d)_butanone Among the following, the compound that can be most readily sulphonated is (1982) (@)_ benzene (6) nitrobenzene (©) toluene (@) chlorobenzene The compound 1, 2-butadiene has (1983) (@) only sp hybridized carbon atoms (©) only sp? hybridized carbon atoms (6). both sp and sp” hybridized carbon atoms (@)_ sp, 3p? and sp? hybeidized carbon atoms Which ofthe following compounds will exhibit cis-trans (geometrical) isomerism? (1983) (@)_2-butene (0) 2-butyne (©) 2-butanol (@ butanal ‘The IUPAC name ofthe compound having the formula CHs Hyc-C-CH=CH, oy is (1989 (@)_3,3,3-Trimethyl--propene (0) 1,1, leTrimethyl-2-propene (©) 3,3-Dimethy-I-butene (8) 2,2-Dimethy-3-butene ‘Anisomer ofethanol is (@) methanol (6) diethylether (©) acetone (@ dimethyl ether ut of the following compounds, which will have a zero dipole moment? (1987) @) 1, L-dichloroethylene (©) cis-1,2-dichloroethylene (©) trans-1,2-dichloroethylene (6) None of these compounds (1986) GP_3021nd 10. uw n 13, 4 15, 16 1”. 18, 19. 20. —_ Tropiie-wise Solved Papers «CHEMISTRY ‘The bond between carbon atom (1) and carbon atom (2) in compound N= C- CH=CH, involves the hybrids as (1987) (@) Pandy? (0) sp and sp (© spandsy? (@) spandsp The IUPAC name ofthe compound (1987) ‘CH, =CH-CH(CH,), is (@)_1,1-dimethyl2-propene (b) "3-methyl I-butene (©) 2-vinylpropane (@)_1-isopropylethylene The number of isomers of C,H, is (1987,2007) @ 4 ) 5 © 6 @ 7 The Cl—C—CI angle in 1,1,2,2-tetrachloroethene and {etrachloromethane respectively will be about (1988) @) 120%and 109° (6) 90°and 109.5° (©)_109.5%and90° (8) 109.S%and 120° InCH,CH,OH, the bond that undergoes heterotic cleavage most readily is (1988) @ cc () co © CH @ OF The compound which has one isopropyl group is (@)2,2,3,3.teramethyipentane (2989) (b) 2,2-dimethyipentane (©) 2,2,3etrimethylpentane (@) 2-methylpentane ‘The C-H bond distance isthe longest in (19s) (@) Gh ) GH, © CH, @) GHB ‘The number of sigma and pi-bonds in I-butene-3-yne are (1989) (a) Ssigmaand5 pi (©) 7sigmaand 3pi (©) 8sigmaand2 pi (@ Ssigmaand 4 pi ‘The compound which gives the most stable carbonium ion ‘on dehydration is (1989) ti) @ Cih-CH-cHpH @) CHh-C-OH CH, CHy (©) CH,—CH,—CH,~CH,OH (@ Ciy-CH-Ch- Ch on The hybridization of carbon atoms in C-C single bond of HC=C-CH=CH,is 99) (@) sp—sp" (b) sp? sp* © 9-sr @ psp ‘The products of combustion ofan aliphatic thiol (RSH) at 298K are (1992) (@) CO,(g), H,O(g) and $O,(g) (0) CO,(), H,OD andSO,(g) (©) COD, H,OandSO,(g) (@) CO,@), H,Oands0,() a 28, 6. 2. Isomers which can be interconverted through rotation around a single bond are (1992) (a) Conformers (6) Diastereomers (©) Enantiomers (@)_ Positional isomers He, H Thestvcture Noe ; shove ce nc Nc [coon bu, (a) geometrical isomersism (1995S) @ Seolimminn (c) geometrical & optical isomerism (d)_ tautomerism. Allyl isocyanide has. (1995S) (@) Sand 4 bonds (0) 8.and Sx bonds (©) 90, 3nand2 non-bonded electrons (@ 80, 3nand 4 non-bonded electrons Arrange in order of decreasing trend towards S, reactions (19955) CChlorobenzene, benzene, aniliniumchleride, toluene 1 in OI Vv (a) I>I>II>IV (© ener Most able carbon on is (@) p-NO,—C,H,—CH,* () Ckct (©) p—CHC ih —cH,* @) p-Cio“c4—CH,* Inthe following compounds, oH OW cy o w The order of acidity is @ M>Iv>I-m () 1e1v>mET (©) I>I>m>v (@ I>m>i> Arrange the following compounds in order of increasing () l>i>u>Iv (@ > u>m>Iv (19955) (1996) oH yo, ay oH NO; w) dipole moment. (1996) Toluene (1) ‘m-dichlorobenzene (II) ‘o-dichlorobenzene III) __p-dichlorobenzene (IV) @ I ‘The optically active tartaric acid isnamed as D-(+)—tartarie acid because it has a positive (199) (@)_ optical rotation and is derived from D-glucose (6) pHin organic solvent (©) optical rotation and is derived from D ~ (+) ~ glyceraldehyde (@ optical rotation only when substituted by deuterium, Which ofthe following compounds will exhibit geometrical isomerism? (20008) (@) 1-Phenyl-2-butene _(b)_3-Phenyl-I-butene (©) 2-Phenyl-I-butene —__(d)_1,1-Diphenyl-I-propene Which of the following has the highest nucleophilicity? @ Fr ©) on 2000) © cH @ Nay ‘The order of reactivities of the following alkyl halides for a Syy2 reaction is (2000) (@) RF>RCI>RBr>RI_— (6) RF>RBr>RCI>RI (©) RCI>RBr>RF>RI—(@)_-RI> RB>RCI> RF Which of the following has the most acidic hydrogen ? (20008) (@) 3-Hexanone (6) 2,4-Hexanedione (©) 2,SHexanedione __(@)_2,3Hexanedione The number of isomers for the compound with molecular formula C,BrCIFLis (20018) @ 3 &) 4 5 @ 6 ‘An Sy2 reaction at an asymmetric carbon of a compound always gives (2001s) (@)_ an enantiomer ofthe substrate (©) a product with opposite optical rotation (©) amixture of diastereomers (@) single stereoisomer Which of the following compounds exhibits stereoisomerism? (20028) (@) 2-methylbutene-1 ——(b)_3-methylbutyne-1 (©) 3-methylbutanoic acid (4) 2-methylbutanoic acid Which of the following acids has the smallest dissociation constant ? (20028) (@) CHCHFCOOH (0) FCHCHCOoH (©) BKCH,CH,COOH = (@)_ CHLCHBICOOH Identify the correct order of boiling points ofthe following compounds, (20028) CH,CHLCH,CHLOH,.cH,CH,.CH,cH0,cH,CH,cH, COOK (@ 1>2>3 (b) 3>1>2 (©) 1>3>2 (@ 3>2>1 Identify the correct order of reactivity in electrophilic substitution reactions of the following compounds (20025) a 2 45. cH, 1 2 (@) 1>2>3>4 () 4>3>2>1 (©) 2>1>3>4 (@ 2>3>1>4 Which of he following hydrocarbons has the lowest dipole xo, O° ‘moment? (20025) 146 Hy rs L () cHyc=ccH, uu (9) CHCH;C=CH (CH; =CH-C=CH Which of the following represents the given mode of hybridisation sp? — sp? — sp— sp from left to right? (20035) fi (@ M,C=CH-Cc=N —@ HIe=c-c ech © Hc Hy @) HCA? Among the following, the molecule withthe highest dipole moments: (20038) @ cHC & CHA, (©) CHO, @ Col, In the given conformation, if C, is rotated about C, - C, bond anticlockwise by an angle of 120° then the conformation obtained is (20045) (@)_fullyeclipsed conformation (b)_ partially ectipsed conformation (©). gauche conformation (@) staggered conformation Which ofthe following resonating structures of I-methoxy— 1,3-butadiene is least stable? (20058) 2 2 (@ Ci; ~CH=CH-CH=0-CHs ° ® (b) CH=CH -CH-CH=0-CHy 2 8 () Chy-CH-CH=CH-0-CH; ° @ (@) Cih=CH- CH-CH-0-CHy46. a7. 48. ‘Hs CH; CHy om Oy» HCl GH compound on hydrolysis in aqueous acetone will give (20058) ci CH) CH (i) CH3O- (Oy HOw Gi, cits CH CHs «iy cnoXo1 NO: on HCH Hy CH CH HCH on (@) Mixtureof(i)and (i) (b) Mixture of(i) and (ii) (©) Only(iiy (a) Only(i) ‘The IUPAC name of C,H,COCl is (@)_ Benzene chloro ketone (6) Benzoyl chloride (©) Chloro phenyl ketone (@ Benzene carbonyl chloride Inthe following reaction, ° Cone. HNO, | ‘Co. S04 H the structure of the major product "X' is aw » Ds I ) 7 I } Ow TO. Y he, (2006 - 3M, -1) 2007) Topic-wise Solved Papers - CHEMISTRY ® wks H 49. Among the following, the least stable resonance structure is (2007) Za W i 9 8 aan ae 3 8 2 @ ae? 50. ‘The number of stereoisomers obtained by bromination of trans-2-butenes 2007) @ 1 (b) 2 3 @ 4 51. _Hyperconjugation involves overiap ofthe fllowing orbitals fa) oo (0) o-n (2008) © PP (d) mm 52, The correct stability order forthe following species is (2008) d @ 2 A AA AA Yo ON o a ay w (@) d)>v)>@>al — &) >dh>«alh>av) (©) dh>(>av)>(l) (a) (> al>ah>"v) 53. The IUPAC name of the following compound is. (2009) OH a (2) 4-Bromo-3-cyanophenol (b) 2-Bromo-5-hydroxybenzonitrile (©) 2-Cyano-4-hydroxybromobenzene (8) 6-Bromo-3-hydroxybenzonitrileOrganic Chemistry — Some Basic Principles and Techniques —_________________» ‘54, In the following carbocation, H/CH, that is most likely to rigrate to the positively charged carbon is (2009) bake n¢—¢—¢—C_—Ga, HO OH CH, (@ Chiatc4 ©) Hac (©) CH atC2 @ Hace 85. Among the following compounds, the most acidic is eon (@)_ prnitrophenol (6) _p-hydroxybenzoic acid (©) o-hydroxybenzoicacid (4) p-taluicacid 56, Klin acetone, undergoes Sy? reaction with each of P,Q, R and S. The rates of the reaction vary as (JEE Adv. 2013) ° a H,C-cl )-a Q>R>S (b) S>P>R>Q (@ P>R>Q>s (6) R>P>S>Q D BRR uenteanes 1. Resonance structures of a molecule should have (@) identical arrangement of atoms assy, (b) nearly the same energy content (©) thesame number of paired electrons (@) identical bonding 2. Phenol s less acidic than (1986) (@) aceticacid (b) _p-methoxyphenal (©). prnitrophenol (@) ethanol 3. Dipole moment is shown by (1986) (2) 1,4-dichlorobenzene (b) cis- 1,2-dichloroethane (©). trans-1,2-dichloroethene (@)_trans- 1,2-dichloro-2-pentene 4. Only two isomeric monochloro derivatives are possible for: (1986) (a) mbutane (b) 2,4-dimethylpentane (c)_ benzene (d)_ 2-methylpropane Which ofthe following have symmetric carbon atom? (1989) Cl Br HC ; @ ween We-fa k hh HH © n-¢-G-cH,c1 it (@® H-C-C-cHy Ha br 0 Br OW 59 6. What is the decreasing order of strength of the bases OHT,NH3,HC=C™ and CH3CH3? (1993) (@) CH, ~CHy > NH >H-C= ~ > OH (©) H-C=C" > CH;—CH5 > NH > OH (© OW > NH > H- > CH, -CHy (8) _NH3 >H-C=C” > OH” > CH; ~CH3 7. Which of the following compounds will show geometrical isomerism? (1998) (@) 2-butene (©) propene (©) 1-phenylpropene (d)__2-methyl-2-butene 8, Among the following compounds, the strongest acid is (1998) (@) HC=cH © Co © CH, @ cy 9. Tautorerism is exhibited by (1998) (b) O= C)~ een 1999) (a) have 4n x electrons (b) have(4n+2)melectrons: (©) beplanar (d)_ be cyclic AL, The correct statements(s) concerning the structures E,F and Gis (are)— wu He. Oo | WC __on (E) cy (@)_E,F,andG areresonance structures (6) EFandE, Garetautomers (©) FandG are geometrical isomers (@) Fand Gare diastereomers 12, The correct statements) about the compound given below is(are) (2008) CL oll Shy Hoa a (@) The compound is optically active (6) The compound possesses centre of symmetry (©) The compound possesses plane of symmetry (4) The compound possesses axis of symmetry H—_ Tropiie-wise Solved Papers «CHEMISTRY 13, The correct statements) about the compound H,C(HO)HC-CH=CH—CH(OH)CH, (X)isfare) (@) The otal numberof stereoisomers possible for X is 6 (6) The total number of diastereomers possible for X is 3 (6) Ifthe stereochemistry about the double bond in X is trans, the number of enantiomers possible for X is 4 (@ Ifthe stereochemistry about the double bond in X is is, the numberof enantiomers possible for X is2 14, Inthe Newman projection for2,2-dimethylbutane (2009) HC. cH, H 1 y X and ¥ can respectively be (@) Hand (©) CH,and (2010) (6) Handcyn, (@) CHyandcit, 18, Amongst the given options, the compound(s) in which all, the atoms are in one plane in all the possible conformations (ifany),is (are) ear) H w—eec— (@) H—cac— wy (© H,C=c=0 (@ H,C=C=cH, 16. Which of the following molecules, in pure form, is (are) ‘unstable at room temperature? 2012) (a) oO (b) ° 9 l A +d 17. Which ot the given statement(s) about N, O; Pand Q with respect to M is (are) correct ? 2012) a HO HOY H oH Ho /C1 nn /G H Nor Lu a a M N iS cH 18, cH, cH, Hy, OH Ho. H Ho, H HO H a a P Q (@) MandNarenon-mirror image stereoisomers (b) Mand Oare identical (©) Mand Pare enantiomers, (@) Mand Qareidentical ‘The hyperconjugative stabilities of tert-butyl cation and 2-butene, respectively, are due to (JEE Adv. 2013) (2) 6>p(empty) and o -+ x* electron delocalisations (b) 6->6*ando->-nelectron delocalisations (©) 6 p(filled) and o> nelectron delocalisations (@) p (filled) -» 6* and o ->-x* electron delocalisations 5 EO Arrange the following in (0. Increasing reactivity towards HCN (1985) CH,CHO, CH,COCH,, HCHO, C,H,COCH, (i) n-butane, n-butanol, n-butyl chloride, isobutane in increasing order of boiling point. (1988) (iti) benzene, toluene, methoxybenzene, chlorobenzene in increasing order of reactivity towards sulphonation with fuming sulphuric acid, (1988) (iv) Increasing order of acid strength 9) CICH,COOH(), CH,CH,COOH(), CICH,CH,COOH ID), (CH), HCOOH AV), CH,COOHY) () Increasing reactivity in nucleophilic substitution reactions (1992) CH,F, CH, CHBr, CHCL (Write the IUPAC name of: (1986) CH,CH,CH=CHICOOH (ii) Givethe IUPAC name ofthe following compound (1990) Me 7 me Me Me Me (te = Metty (iii) Write the TUPAC name forthe followingOrganic Chemistry — Some Basic Principles and Techniques —_________________» «99y cH I HyC-N- C-CH,CHs H3C Cols For nitromethane molecule, write structure(). () showing significant resonance stabilisation. (1986) (i), indicatng tautomerism (1986) Give reasons forthe following (Carbon oxygen bond lengths in formic acid are 1.234 land 1.36A and both the carbon oxygen bonds in soxium formate have the same value ie. .27A. (1988) (ii) Phenyl group is known to exert negative inductive ‘effect. But cach phenyl ring in biphenyl (C,H,—C,H,) is more reactive than benzene towards electrophilic substitution (1992) (it) Aryl halides are less reactive than alkyl halides towards nucleophilic reagents 99g, (i) CH=CH" ismorebasicthan HC (©) Normally, benzene gives electrophilic substitution reaction rather than electrophilic addition reaction although it has double bonds Write the structural formula of 4-chloro-2-pentene. (1988) Write tautomeric forms for phenol (1992) ‘Write down te structures ofthe stereoisomers formed when cis-2-butene is reacted with bromine. (1995) Discuss the hybridisation of carbon atoms in allene(C,H,) and show the x-orbital overlaps (1399) [dentfy the pairs of enantiomers and diastereomers from the following compounds I, I and IIT (2000) chy cH, cH, i OH O#- HOF H on. HOH: HH OH cu, cu, cu, 1 m Which one is more soluble in diethyl ether - anhydrous AICI, o hydrous AICI,” Explain in terms ofbonding, (2003) 2 1B. Mw Ky (a) Benzoicacid 64x 10% © o—{\—coon sass © ot \—eom woasios © 500—£ \—coon ss asa t (Hots = 1% Where ji; is the dipole moment of a stable conformer of the molecule, Z—CH,—CH,-Z and , isthe mole fraction ofthe stable conformer, Given fgg = LOD andy = 0.82 Drawall the stable conformers of Z ~ CH, ~ CH, ~Z and calculate the value Of ese (ii) Draw the stable conformer of Y - CHD ~ CHD ~ Y (meso form), when Y = CH, (rotation about C, ~C;) and Y = OH (rotation about C, ~ C,) in Newmann projection (2005)__ Topiic-wise Sotved Papers - CHEMISTRY F Eto ‘Each question contains statements given in two columns, which have to be matched. The statements in Column-Lare labelled A, B,C and D, while the statements in Column-II are labelled p, q, rs and 1. Any given statement in Column-I can have correct matching with ONE OR MORE statement(s)in Colunn-II, The appropriate bubbles corresponding to the answers 10 these questions have 10 be darkened as illustrated in the following example Ifthe correct matches are A-p, s and t; Bq and r: C-p and q; and D-s then the correct darkening of ‘bubbles will look lke the given. Given below are certain matching type questions, where two columns (each having 4 items) are given. Immediately after the ‘columns the matching grid is given, where each item of Column I has to be matched withthe items of Column I, by encircling. the correct match(es). Note that an item of Columa I can match with more than one item of Column IL All the items of Column HT must be matched. Match th following (2006 -6M) Column Column (A) C,H,CH,CD,Br on reaction with C,H,O™ gives (©) El eaction CMe CHECD, (B) PACHBICH, and PhCHBYCD,, both react with (@) F2reaction the same rate (© C,H,CH,CH,Bron treatment with C,H,O°and (© EleBreaction C,H,OD gives C,H,CD=CH, (©) C,H,CH,CH,Br reacts faster than CHjCD,CH,Br (5) Firstorder reaction ‘on reaction with C,H,O~in ethanol 2. Match the compounds/ions in Column I with their properties/reactions in Column I. Indicate your answer by darkening the appropriate bubbles of the » 4 matrix given in the ORS. (2007) Column Column tt (A) CHJCHO ()_sives precipitate with 2, 4-dinitrophenythydrazine ®) CHC=CH (@ gives precipitate with AgNO, ow (© isanucleophile Or (6)_isinvolved in eyanohydrin formation 3. Match each of the compounds given in Columa-I with the reation(s), that they can undergo, given in Columntl. (2009) Cotumn-t ‘Column Br “ cy (®) Nucleophilie substitution o- ‘OH ® (@) limination cho oC «vatican on Br » Co (6). Estericaton with etic anhyéride NO, (DehydrogenationOrganic Chemistry — Some Basic Principles and Techniques 4. Match the reactions in Column I with appropriate types of steps/reactive intermediate involved in these reactions as given in Column I, Column 1 Wc. 0 ov. Noo “ | D ¢ (2011) (Column 1 0 (p) Nucleophilic substitution (@) Electrophilie substitution (#) Dehydration Oo (s)Nucleophilic addition ne Now, (9) Carbanion BH E@roeees «= terete Read the following Statement-I(Asseration) and Statement -2 (Reason) and answer as per the options given below (@)_Ifboth Statement -1 and Statement -2 are correct, and Statement -2 is the correct explanation of the Statement 2. Ifboth Statement -1 and Statement -2 are correct, but Statement -2 is not the correct explanation of the Statement-1 (©) 1fStatement-1 is correet but Statement-2 is incorrect. (@)_1fStatement 1 is incorrect but Statement? iscorrect. 1. Statement: Ary halides undergonucleophilic substitution with ease. Statement -2:The carbon-halogen bond in aryl halides has partial double bond character. (1991) Statement -1: Phenol is more reactive than benzene towards electrophilic substitution reactions Statement-2:In the case of phenol, the intermediate carbocation is more resonance stabilized, (20008) 3. Statement -1: Molecules that are not superimpossable on their mirror images are chiral, ‘Statement 2: All chiral molecules have chiral centres. (2007) © ‘The total number of cyclic structural as well as stereo isomers possible fora compound with the molecular formula CH is (2009) The total number of cyclic isomers possible for a hydrocarbon with the molecular formula C,H, is 5. (2010) ‘The maximum number of isomers (including stereoisomers) that are possible on monochlorination of the following, ‘compound is ou) cH, cucu | CHC, 4 ‘The total number of contributing structures showing hyperconjugation (involving C-H bonds) forthe following catbocation is 2011) H.C_@ —cH CH,or) ‘S. The total number(s) of stable conformers with non-zero dipole moment forthe following compound is (are) (JEE Adv. 2014) ci bf cn, b—fea oy, II Section-6 {TTT 1. Arrangement of (CH,),C-, (CH,),CH, CH,—CH,—when attached to benzyl or an unsaturated group in increasing order of inductive effect is [2002] (@) (CH),C-<(CH),CH- ethyl btanoate (0) CHy~ GH-Cilp ~CHO > 3methy-buanal cH (©) CH3~ CH ~ CH—CH, -> 2-methyl-3-butanol I OH CH __ Topiic-wise Sotved Papers - CHEMISTRY 6. The total number of stereoisomers that can exist for M is (JEE Adv. 2015) HC CH, HC ° @ chy -arban ~CHy ~ 2-methy-3-pentanone chy The IUPAC name of CH,COCH(CH) (@)_ 2-methy-3-butanone (©) 4-methytisopropyl ketone (©). 3-methy/-2-butanone (@_Isopropylmethyl ketone In which ofthe following species is the underlined carbon having sp* hybridisation? [2002], (@ CH,COOH (®) CH,CH,OH (©) CH,COcH, (@ CH,=CH-CH, Racemic mixture is formed by mixing two (@) isomeric compounds (6) chiral compounds (©) meso compounds (@_ enantiomers with chiral carbon Following types of compounds (as I, II) 2003] [2002] (2002) cuycH=cict cHCHOH T I Guycn, u sre tied inten of isomerism in (0) cainisorersm ——(&)_ pasion isomerism (©) conformers (d)_stereoisomerism ‘The reaction: (2002) (cuy,c-Br 225 (cry,c-on (a) elimination reaction (b) substitution reaction (©) free radical reaction (d)_ displacement reaction.