RANK Resonance MTaiksi a} Distance Learning Programmes Division (DLPD} ™ Redefined 1000+ Performance Boosters.. TT ye ee strengthen & clarify the concepts. Topic Wise 1000+ Questions. 6 Part Syllabus Test. 3 Full Syllabus Test. Covers Class XI & Class XII Syllabus. Complete Solutions. vvvvy CHEMISTRYo> Chem ot Contents SECTION-I (TOPIC WISE PROBLEMS) 2 JEE (Advanced) - RRB a S.No. Topic Page No. PHYSICAL CHEMISTRY 1. ELECTROCHEMISTRY 001 - 007 2, IONICEQUILIBRIUM 008-013 3. SOLUTION& COLLIGATIVE PROPERTIES 014-019 4. CHEMICALKINETICS & RADIOACTMITY 020-028 5. STOICHIOMETRY 029-034 6 THERMODYNAMICS & THERMOCHEMISTRY 035 - 042, 7. SOLID STATE 043-048 8 CHEMICAL EQUILIBRIUM 049 - 056 9 GASEOUS STATE 057 - 065 10. ATOMIC STRUCTURE 066-072, 11, SURFACE CHEMISTRY iM 073-078 INORGANIC CHEMISTRY 4. PERIODIC TABLE & PERIODICITY 079-083 2. CHEMICAL BONDING 084-080 3. COORDINATION COMPOUNDS 091 - 097 4. METALLURGY 098 - 103 5. s-BLOCK ELEMENTS & THEIR COMPOUNDS, 104-107 6 p-BLOCK ELEMENTS & THEIR COMPOUNDS 108-111 7, d-& f BLOCK ELEMENTS & THEIR COMPOUNDS 112-116 8. ~ QUALITATIVEANALYSIS 417 - 122 ORGANIC CHEMISTRY 4. IUPACNOMENCLATURE AND ISOMERISM (GOC-)) 423 - 130 2 GENERALORGANIC CHEMISTRY 131-138 3 REACTIONMECHANISM 199-148 4, GRIGNARDREAGENT, REDUCTION & ALKANE 149-159 5, ALKENE, ALKYNE AND OXIDATION 160-170 6 AROMATIC COMPOUNDS. 471-185 7. POC-1& STRUCTURAL IDENTIFICATION 186 - 195 8 ALDEHYDES AND KETONES 196-207 9. CARBOXYLICACIDS & ACID DERIVATIVES 208 - 219 10. BIOMOLECULES AND POLYMERS 220 - 227 11. PHYSICAL PROPERTIES & POC.I 228 - 233 PN Resenence ——_—__—— aNTUMNAATNUTTTTN NNTB TiccczitieecSaUTITTT Gaal5 Chemisry.a Contents 10 JEE (Advanced) - RRB ca SECTION-II (PRACTICE TEST PAPERS) Particular Page No. Resonance. dvening fo bt omer 6 PTs (PART TEST) PT-01 (PHYSICAL CHEMISTRY: CLASS-xI) % PT-02 (INORGANIC CHEMISTRY : CLASS-XI) ‘© PT-03 (ORGANIC CHEMISTRY: CLASS-XI) ‘+ PT-04 (PHYSICAL CHEMISTRY : CLASS-XIl) ‘+ PT-05 (INORGANIC CHEMISTRY : CLASS-XIl) ‘+ PT-08 (ORGANIC CHEMISTRY : CLASS-XII) 3 FST (FULL SYLLABUS TEST) ‘+ FST-01 (CLASS XI SYLLABUS) ** FST-02 (CLASS Xil SYLLABUS) *s FST-03(CLASS XI + CLASS XII SYLLABUS) 234-240 244 - 245 246 - 252 253 - 260 261 - 266 267 - 275 276-279 280-284 285-2921 Chemisery co Answers & Solutions SECTION-| (TOPIC WISE PROBLEMS) 1s JEE (Advanced) ~ RRB ca S.No. Topic Page No. PHYSICAL CHEMISTRY —- 4. ELECTROCHEMISTRY 293-301 2 IONICEQUILIBRIUM 302-306 3. SOLUTION & COLLIGATIVE PROPERTIES, 307-312 4. CHEMICAL KINETICS & RADIOACTIVITY 313-320 5. STOICHIOMETRY 320-328 6 THERMODYNAMICS & THERMOCHEMISTRY 328-334 7. SOLID STATE . 335-340 8 CHEMICAL EQUILIBRIUM 340-346 9. GASEOUS STATE 347-354 10. ATOMIC STRUCTURE 354-361 11. SURFACE CHEMISTRY 361-364 INORGANIC CHEMISTRY 4. PERIODIC TABLE & PERIODICITY 365-368, 2 CHEMICAL BONDING 368 - 379 3. COORDINATION COMPOUNDS 379-389 4. METALLURGY 389-394 5, BLOCK ELEMENTS & THEIR COMPOUNDS 395-399 6. p-BLOCK ELEMENTS & THEIR COMPOUNDS 399 - 404 7. d- &f-BLOCK ELEMENTS & THEIR COMPOUNDS 404-410 8 QUALITATIVEANALYSIS. 410-416 ORGANIC CHEMISTRY . 1. IUPAC NOMENCLATURE AND ISOMERISM (GOC-)) 4t7 424 2, GENERAL ORGANIC CHEMISTRY 421-426 3. REACTIONMECHANISM 426 - 431 4, GRIGNARD REAGENT, REDUCTION & ALKANE 432-437 5. ALKENE, ALKYNE AND OXIDATION 437 - 445 6 AROMATIC COMPOUNDS: 445- 454 7. POC+| & STRUCTURAL IDENTIFICATION 454-461 8. ALDEHYDES AND KETONES 461 - 470 8. CARBOXYLIC ACIDS & ACID DERIVATIVES 470-478 10. BIOMOLECULES AND POLYMERS 478-482 11, PHYSICAL PROPERTIES & POC-II 482-485.© * Chimistry a 1 JEE (Advanced) -RRB ca Answers & Solutions SECTION-II (PRACTICE TEST PAPERS) Particular Page No. © 6 PTs-(PART TEST) & PT-01 (PHYSICAL CHEMISTRY : CLASS-XI) 486 - 490 oe PT-02 (INORGANIC CHEMISTRY : CLASS-XI) 491-495, e PT-03 (ORGANIC CHEMISTRY : CLASS-X!) 495 - 497 > PT-04 (PHYSICAL CHEMISTRY : CLASS-Xil) 498 - 503 + PT-05 (INORGANIC CHEMISTRY : CLASS-XI!) 504 - 509 * PT-06 (ORGANIC CHEMISTRY : CLASS-XIl) 509-513 oO 3 FST (FULL SYLLABUS TEST) o FST-01 (CLASS XI SYLLABUS) 514-515 _ FST-02 (CLASS XII SYLLABUS) 516-518 ‘ _ FST-03(CLASS XI + CLASS XIFSYLLABUS) 519-525 - PA Resecense SsOnsance.SINA18Odd ASIM DIdOL I-NOILIAS5 Chemistry TOPIC 1 SECTION -|: STRAIGHT OBJECTIVE TYPE 1.4 The reduction potential of hydrogen haf cel willbe negative f(T = 298 K) (A) Phy = 4 atm and [H4] = 4.0 M (8) Pa =2atm and [H"] = 2.0 M (C) Pa, = 2atm and [H4]=1.0M (0) Ph, = atm and [H"] = 2.0 M JEE (Advanced) - RRB ca ELECTROCHEMISTRY 4.2. Avery hin copper plate is electro-plated with gold using gold chloride in HCI. The current was passed for 20 minutes and the increase in the weight of the plate was found to be 2 gram (Au = 197]. The current passed was (A) 0.816 amp. (©) 1.632 amp. (C)2.448 amp. (0)3.264 amp. 13° Gwen ()MnO~ + 8H* + Se —> Mnt + 4H,0 (i) MnO, + 4H +2e- —> Mn+ 2H,0 Find E° forthe following reaction MnO; + 4H" + 3e- —> MnO, +2H,0 x=, @)x, © 1.4 The solubility of [Co(NH,),Cl CIO, Me Recguigycty = resistance was 33.5 22 in a cell with cell constant of 0.20 is (A)59.75 mmol. (B) 48.75 mmovl. (6) 38.75 mmol. (D) 28.75 mmol. 4.5 Wehave taken a saturated solution of AgBr. K,, of AgBris 12 10-. If 10-7 mole of AgNO, are added to + lite of his solution then the conductivity ofthis solution in termes of 10°? Sm unite will be [Given Xi, =4% 109 Sm? mot! ry, #6 102S mémor, Ayo, = 5% 10°Sm# mob] (a)39 55 (cts (oat 1.6 ‘The specific conductivity of an aqueous solution of a weak monoprotic a¢id is 0.00033 ohm-tcm~ at a concentration 0.02 M. if tthis concentration the degree of dissociation is 0.043, then calculate the vale of ‘Ag(in ohn cm? feqt) (a)as3 (3438 (ose er] 17 Atwhat does the folowing cell have its reaction at equilibrium? joo ‘9 z Ag(s) | Ag,CO,(s) | Na,CO, (aa)! | KEr(aq)| AgBr(s) | Agts) Kop = 8 * 10"? for Ag,CO, and K,,= 4 « 10-18 for AgBr (a) Fi 107 (8) v2 «107 (©) 8 «107 (0) V4 «107 Cr,0F 4.8 For the cell prepared from lectode And B, electrode: EG, e®, = + 1.99 Vand electrode B Fe Few + (2 =0.77 V, which ofthe folowing statement is not correct? (A) The electrons will flow from B to A (in the outer circuit) when connections are made. (B) The standard e.m-f. of the cell wil be 0.56 V. (C) Awillbe positive electrode. (D) None of the above. PN Sesenen¢@ a8 Chemt—9 8 ir JE (Acranced)- RRB 4.9 Aceticacid has K, = 1.8 x 10*while formic acid has K,=2.1 x 10“. What would be the magnitude of the emf of the cell PtH.) PtH2) at 25°C? 0.1 M sodium acetate| [0.1 M sodium formate (A) 0.032 volt (8) 0.063 vol (C) 0.0456 vort (0) 0.055 vott 4.40 Consider the cellAg(s)/Agir(sr-(aq)l C(aq) | AgC(s) | Ag(s) at 25°C . The solubilty product constants of AgBr BAgClare 5 x 10" & 1 x 10" respectively. For what rato of the concentrations of Br & CI ions ‘would the emf ofthe cell be zero ? (ayt:200 ~ (8) 1: 100 (c)1:500 (0)200:1 4.11 Fora saturated solution of AgCl at 25°C, k = 3.4 x 10% ohm” cm" and that of H,O (¢) used is 2.02 10 ohm” cm. 2°,, for AgC! is 138 ohm cm? mot", then the solubilty of AgClin moles per liter wil be: (ayto* (8) 10 10" (0) 10" 4.12 Accurrent of 0.1A was passed for 4hr through a solution of cuprocyanide and 0.3745 g of copper was deposited on the cathode. Calculate the current efficiency for the copper deposition. (Cu ~ 63.5) (A) 79% (8) 39.5% (63.25% {0)63.5% 1.13. With ttaken in seconds and | taker in Amp, the variation of folows the equation b+ P= 25 what amount of Ag will be electrodeposited with this current flowing in the interval 0-6 second (Ag :—108)? (A)22 mg (8) 66mg (€)77 mg (©) 88mg (0.1M acetic acid + | (0.1.M formic acid len**aa}| HChaq3] Hotoll Ptwith E,., = 0.701 and oom 10m 10am You are given the following cell at 298 K, 2n| Ef, /2n =—0.76 V. Which ofthe following amounts of NaOH (equivalent weight= 40) wilust make the pH ‘of cathodic compartment to be equal to 7.0 (A)04 grams (B)4 grams (C)10grams (0)2grams 1.45 Aresistance of 509 is registered when two electrodes are suspended into a beaker containing a dilute solution of a strong electrolyte such that exactly half ofthe them are submerged into solution, Ifthe solution is diuted by adding ure water (negligible conductivity) so as to just completely submerge the electrodes, the new resistance offered by the solution would be (A502 (8) 1009 (c)25a (0)2000° 1.46 The standard reduction potential of a AgCV/Ag electrode is 0.2 V and that of a silver electrode (Ag'/Ag) is 0.79 V. The maximum amount of AgC! that can dissolve in 10° L of a 0.1 MAgNO, solution is {A)0.5 mmol (8) 1.0 mmol (C)2.0 mmol (0)2.5mmol 4.47 Calculate the cell EMF in mV for Pt | H,(1atm) | HCI (0.01 M) | AgCl(s) | Ag(s) at 298 K AG? values are at 25°C kb = 109.56 = for AgC\(s) and kd ~ 130.79 for (H* + Cr) (aq) (A) 456 mv (2) 654 mv (C)646.mv (O)None of these, N Sesenence —____________—____yaf2 Ohemisiry ca 1.48 41.49 1.20 421 1.22 TEE (Advanced) - RRB ca Value of A,,° for-$rCl, in water at 25°C from the following data Cone. (mott) 05 4 Ay(G'em? mot!) 280 250 270 (@)260 (©)250 (@)255 Calculate the useful work ofthe reaction Ag(s) + 1/2CL(g) —> AgCi(s) Given Eo cr = + 1.96, E°agagcyor = 0.22 V 1 Poetain and T=206K (A) 110 ku/mol (B) 220 kJ/mot (C) 55 kJ/mol (D) 1000 ku/mol Select the correct statement if - Et ig= AV, Eggert OAV, Boe ne rine = 1SV, Ep 20.5 V Here, (A) Mn0,; is the strongest Oxidizing Agent and Mgis the strongest Reducing Agent (8) Sn** + 2+ —> Sn? | is a spontaneous reaction. (©) Mg? + Sr’* —> Mg + Sn* is a spontaneous reaction. (©) Here, Weakest oxidizing agent is Sn and weakest reducing agent is Mn* AcellAg | Ag" Cu" | Cuintaly contains 2M Ag* and 2M Cu" ions. The change in cell potential after the passage of 10 amp current for 4825 seois ()-0.0074 (®)-1.00738V—(C)-0.0038V (0) none For the cell (at 298 K) Ags) | AgCi(s) | CI-(aq) || AgNO, (aq) |Ag(s) ‘Which of foliowing is correct - (A) The cell emf willbe zero when ([Ag*] in anodic compartment = [Ag'] in cathodic compartment) (8) The amount of AgCK(s) precipitate in anodic compartment will decrease with the working of the cell. (C) The concentration of [Ag'] = constant, in anodic compartment during working of cel eo (©) Ear = Faring “E6r noe Aa ~ SECTION - Il : MULTIPLE CORRECT ANSWER TYPE 1.23 4.24 ‘Acurrent of2.68 Ais pasted for one hou’ through aii aqueous Solution of CuSO, using coppérelectrodes Select the correct statement(s) trom the following : (A) increase in mass of cathode = 3.1749 (8) decrease inemass of anode = 3.174g (C)no changein masses of electrodes (0) the'ratio between the change of masses of cathode and anode is 1:2 Which isfare correct among the followings? 1.337, Ee 8 gy = 0-524 Given, the haif cell ems E2219, (A) Cu" disproportionate. (8) Cuan Cu** comproportionates (reverse of disproportionation into Cut). (©) Ebay cur Eta jou Is positive. (O)Allof these. PN Sesenence ——-_—______—__——_—§— jt© Chemistry cae $$$ $$$ 68 (Advanced) - RRB a. 4.25 The standard redox potentials E* ofthe following systems are System E* (volts) () MnO" + 8H" + Se" Mn" +4H,0 1.51 (@)— S#*# > Snt +26" 0.15 Cr,0,*+ 14H" + o> 2Cr*" + 7H,0 1.33 (w) Co" Cet" +e" ~ 181 ‘The oxidising power of the various species are related as (A) Cr,0;->Mn0,— (8) Cet > Sn* (©) Ce* > Mino, (0) Mno.- > Sn* 1.26 Mark out the correct statement(s) regarding electrolytic molar conductivity (A) Itincrease as temperature increases. (8) Itexperiences resistance due to vibration of ion at the mean position. (C) Increase in concentration decreases the electrolytic molar conductivity of both the strong as well asthe weak electroiyte * (0) Greater the polarity of solvent, greater isthe electrolytic molar conduction. SECTION - Ill : ASSERTION AND REASON TYPE 4.27 Statement-1 : Specific conductance decreases with dilution whereas equivalent conductance increases, Statement-2 : On dilution number of ions per mille decreases but total number of ions increases considerably. (A) Statement-1 is True, Statement-2is True; Statement-2 is a correct explanation for Statement-1 (8) Statement-1 is True, Statement-2 is True; Statement-2is NOT a correct explanation for Statement-1 (C) Statement-+ is True, Statement-2 is False. (0) Statement-1 is False, Statement-2 is True. 1.28 Statoment-t :Zine protect the Iron better than tin even after it cracks. ‘Statement-2: Ep, < Ede, But Eoe,, > Ede, {A) Statement-t is True, Statement 2is True; Statement.2is a correct explanation for Statement-1, (8) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-. (C) Statement is True, Statement-2 i False (0) Statement- is False, Statement-2 is True 1.29 Statement-t : On increasing dilution, the specific conductance keep on increasing. Statement-2 : On increasing dilution, degree of ionization of weak electrolyte increases and mobility of ions also increases. (A) Statement-1 is True, Statement.2 is True; Statement-2is a correct explanation for Statement-1 (8) Statement is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1 (C) Statement-t is True, Statement-2 is False. (0) Statement-t is False, Statement-2is True, 1.30 Statement. © re Egy, Fe electrode act as cathode and Ni electrode actas anode. Statomont2 : Because AG* < 0 and E*,, > 0, s0 cell is possible. (A) Statement is True, Statement.2is True; Statement 2is a correct explanation fr Statement-t (B) Statement- is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1. (C) Statement-t is True, Statement-2 is False. (D) Statement-1 is False, Statemnent-2 is True.2 Ohetnsty $$ 8 (hava) - RRB ce SECTION - IV : COMPREHENSION TYPE Comprehension #4 ‘A fue! cell is a cell that is continuously supplied with an oxidant and a reductant so that it can deliver a currentindefinitely. Fuel cells offer the possibilty of achieving high thermodynamic efficiency inthe conversion of Gibbs energy [nto mechanical work. Internal combustion engines at best convert only the fraction (T,~T,)/T, of the heat of combustion into mechanical work. ag ioe “AH here AG is the Gibbs energy ‘change for the cell reaction and AH Is the enthalpy change of the call reaction. Abhydrogen-oxygen fuel cell may have an acidic or alkaline electroiyte. 2.303RT Pt| Ha(a) | H* (@q,) | Hz(2) | O2 (g) | Pt; —E-- = 0.06 The above fuel cell is used to produce constant current supply under constant temperature & 30 atm constant total pressure conditions in a cylinder. If10 moles H, and § moles of O, were taken intially. Rate of consumption of O, is 10 milli moles per minute. The hatf-cell reactions are, While the thermodynamic efficiency of the fuel cell is given by, F0,(9)+24 (oq) 2° —> Hote) E= 1246 2H" (aq) + 2e- —> Ho) E'=0 ‘To maximize the power per unit mass of an electrochemical cel, the electronic and electroitc resistances of the cell must be minimized. Since fused salts have lower electrolytic resistances than aqueous solutions, high-temperature electrochemical cells are of special interest for practical applications 431 Calculate em. ofthe given cell at = 0, log 2= 0.3) (A) 1255 (8) 1.35 @t1av (0)1.246 1.32 The above fuel cellis used completely as an electrolytic cel with Cu votameter of resistance 26.94 ising Pt electrodes. initially Cu voltameter contains 1 litre solution of 0.05 M CuSO, [H'] in solution after electrolysis (Assuming no change in volume of solution). (a)o.015 Mm (8)0.03M (©)0.025M ()0.01M 1.33 92,2 (CuP)=0.01S m?mole*, 2,(H') =0.035S m? mole" and 3,~(SO,*)= 0.016 Si? mole”, specific Conductivity of resulting solution eftin copper voltameter after above electrolysis is, (2578 rr" (8) 1.75 Sr! (©) 1.5258 mrt (0)225 Sort Comprehension # 2 ‘The mélar conductance of NaCl varies with the concentration as shown in the following table. and all valves follows the equation 28, = aE, -bVE ‘Where 4°, = molar specific conductance 1, = molar specific conductance at infinite ditstion © = molar concentration Molar Concentration Molar Conductance of NaCl in ohm" cm? mole 4x10" 407 9x10" a7 16x10" 7 When a certain conductivity cell (C) was filed with 25 x 10+ (M) NaCI solution. The resistance of the cell was found to be 1000 ohm. At infinite dilution, conductance of Cl-and SO,-*are 80 chm~' cm? mole~tand 160 ohm" cm? mole" respectively. - IR Seserence ———______—_—____—_——gat19 Chemisty ¢—@ $< < ir IEE (Advanced) «RRB ca 1.34 Whats the molar conductance of NaCI at infinite dilution ? (A) 147 ohm cin? mole" (8) 107 ohnr*cm?s mole* (C) 427 ohn’ cm? moet (0) 157 ohne cm? mole 1.35 What isthe cell constant of the conductivity cell (C) (A) 0.385 cr (8) 3.85cm* ()38.5em* (0) 0.1925 em-* 1.36 Ifthe cell(C)is filed with 5 x 10 (N) Na,SO, the obserbed resistance was 400 ohm. What is the molar conductance of Na,SO,, (A) 19.25 ohn cm? mole* (8) 96.25 ohimr* cm? mole (C) 385 ohm cm mote (0) 192.5 ohr*cm’s mole* Comprehension #3 ‘The process of using an electric current to bring about chemical change is called electrolysis. Electrolysis is a process of oxidation and reduction at the respective electrodes due to external current passed in the electrolyte. The prodyct obtained during electrolysis depends on following factors. © The nature ofthe electrolyte hers ‘© The concentration of electrolyte cade «A anode 0) 2 The nature ofthe electrode, Consider the electrolysis of following cell containing iq. solution of CuSO,,ZnCi,andMBr, 9" by using pure silver rod as a cathode and Pt ‘electrode as anode. Assume that M® does not 8 Cur(oq), 16 80,"00) further oxidise and can not form complex with Zesobion 1M Za"(aq), 2MCraq) NH, Assume no hydrolysis of any ion 1 (09) 2M Bra) Phcosted electrode 0 Ag" Ag 2.303 RT _ -oaoy, E H0.34V5 £8, yO, EP a 9 = 0.76 Vs EB gy, =-0828V5 0.06 5 Fouts 100 Ee ne ‘Zn 120 1.37 After passing 20 amp current from battery for 28050 sec. the remaining cone. ofan in solution given in passage would be: (Assume currenteffciency to be 100%), (A) [Cu] = 05M, (MP = 0.5M, [Zn] = 04M (B) [Cu] +O, [NP 0.5m (C) [Cu*] = 05M, [Me] = 0.5M, [2n*]=0.5M —(D) [Cu*] 01M, IM 4.38 Whatillbe the volume of gases formed at anade at STP by electrolysis of above solution after passing 20 amp current for 28950 sec, (Assume current efficiency tobe 100% and one mole of gas occupies 22.4 L volume at STP). (A)44.81 8, (8) 2241.81, (o)224L6, (D)4ABLC, 1.39 If 36molofNH,(g)is passed in electrolytic solution given in comprehension (assume no volume change by addition of NH), then what would be decreasing order of reduction potential of folowing CK [Cu(NH,) = 1 » 10% and K, [zn (NH,),F* = 1 10°} (AYN > Cu > Zn (8) CuP> ME > Zn (C)MP> Zn > Cut (D) Cu > M > Zn SECTION - V: MATRIX - MATCH TYPE 1.40 Match Matrix Column | Column t (A) Zn | Zn*(C) || Zn (2C) | Zn (p) Spontaneous cell reaction {B) H,(P)HCKAN) || H,SO, (1N) | HLCP) (a) Working cell representation (C) Cu] Cu*(0.01M) |] Ag” (0.1M) [Ag (9) Concentration of cation in cathodic compartment increases upto equilibrium. (D) Ag | AgCl | (KCI, 0.1M) || Ag’ (0.01M) | Ag (s) Concentration cell . () Concentration of Cr in anodic compartment decreases. (PN Resececcse — $$$$$_________-++_ar$5 Cheeky 4 in 8 patvancet) RRB ca 1.41 Match the following : Column | Column I 1 (A) Working concentration cell ()H,* 50, 5 H,0 + electrical energy (8) Spontaneous cell reaction (@) E*y= 0 (C) Non - working Daniel cell (Ego 0 (0) Working fuel cet (8) Galvanic cell a (t) For working of concentration cell, concentration of cation in ‘anodic compartment should be less then the cathodic compartment 1.42 Match the column Column Column (A) Molten PbCI, using inert electrode. (p) Metal of salt will reduced (@) Sodium chiotide solution using inertelectrode _(q) H,0+ 26> H,(g) + 20H- (C) Silver nitrate solution with silver electrode. (F) Solution become basic after electrolysis (D) Sodium nitrate solution using inert electrode {s) Solution become neutral after electrolysis (t) Solution become acidic after electrolysis 1.43 Column Column (Quantities) : (Factors on which dependency exist) (A) Molar conductance (0) Temperature (B)emfof acelin operation (a) Concentvation of species involved (C) Electrode potential (Nature of substance involved (D) Standard reduction potential (s) No. of electrons lost or gained in the reaction (dis @ additive property SECTION - VI : INTEGER TYPE 1.44 In the acid base titration [H,PO, (0.1M) + NaOH (0.11) e.m.fof the solution is measured by coupling this electrodes with suitable reference electrode. When alkalis added pH of solution is in acoordance with equation > Eg = Et + 0.059 pH For HPO, Ka,= 10; Ka,= 10%; Ka,= 10 Whats the celle... atthe lind end point of the titration if, at this stage is 1.3805 V. 4.45 The emf. ofa ceil corresponding to the reaction Zn-+ 2H" (aq) —> Zn (0.1M) + H,(g) (1 atm) {80.26 volt at 25°C. Calculate the pH of the solution at the hydrogen electrode, 4.46 Afuel cell uses CH,(g) and forms CO,* at the anode. tis used to power a car with 80 Amp. for 0.96 hr, How many litres of CH,(Q) (at STP, would be required ?(V,,= 22,4 Limol) (= 96500), Assume 100% efficiency. 1.47 For the cells in opposition, 2n(s)|ZnC(sol) | AgGNs) 1A LABCI) | ZAC (6) | Zale) C, = 0.02 M C,=0.5M RT Find out the emf (in millvolt) ofthe resultant cell? (Take log 2 = 0.3, “= at 298 K = 0,060) 1.48 The conductivity of @ solution may be taken to be directly proportional to the total concentration of the charge carries (ions) present init in many cases. Using the above fect find the percent decrease in Conductivity (k) ofa solution of @ weak monoacidic base BOH when its 0.1 M solution is diluted to double its original volume. (K, = 10 for BOH)( take 50 =7.07) (Mark the answerto nearest integer) 49. At0.04 M concentration the molar conductivily ofa solution ofa electrolyte is $000 3-* cm? mot while at 0.01 M concentration the value is 5100 -'cm? mo". Naking necessary assumption (Taking tas strong electrolyte) find the molar conductivity atinfrite dilution and also determine the degree of dissociation of strong electrolye at 0.04 M. u Resonance —— ——_———______—_—_——_— atJEE (Advanced) - RRB ca TOPIC § 2 IONIC EQUILIBRIUM SECTION -1: STRAIGHT OBJECTIVE TYPE 2A Calculate [H'], [HCOO'] and [OCNY in a solution that contains 0.1M HCOOH (Kk, = 2.4 x 10) and 0.4 MHOGN (K,= 4 « 109. (A) [H']= 8 « 102M (8) {HCO} =3 « 10°M (©)[OCN]=5% 109M (O)Allof these 04, amount of Barium acetate to be added to 100 mL of 0.1 M acetic 2.2 To prepare-a buffer solution of pH ‘acid solution [pK,(CH,COO-) = 9.26] (A) 0.05 mole (8) 0.025 mole {C) 0.4 mole (0) 0.005 mole 2.3 1.4589 of Mg reacts with €0.0 mlof a HC! solution whose pH is -0.477. The change in pH when all Mg has reacted. (Assume constant volume. Mg = 24.3 glmol) (log 3= 0.47, log 2 = 0.301) (a) 0.176 (@) +0477 (€) 0.2385 (0)03 2.4 — Find the ApH(initial pH ~ final pH) when 100 mi 0.01 M HCI is added in a solution containing (0.1 mmoles of NaHCO, solution of negligibie volume ( Ka, =10-", Ka, =10-" for H,CO,) (A)6 + 2 log3 (8) 6 ~ log (C)6 + 2log2 (0) 6 ~2log3 2.5 The ionization constant of benzoic acid is 6.46 x 10 and K,, for silver benzoate is 2.5 x 10". How many times silver benzoate more soluble in a buffer of pH = 3.19 2s compared to its solubility in pure water ? (a) 3317 (8) 95 «C) 1000 (75 2.8 30 mi of 0.06 M solution of the protonated form of an anion of acid methonine (H,A‘) is treated with (0.09 M NaOH. Calculate pH after addon of 20 ml of base. pka, = 2.28 and pKa, = 92 55 (B) 5.74 (C) 9.5 (D) None 2.7 The indicator constant for an acidic indicator, HIn is § « 10*M. This indicator appears only in the ePam (Hin) 4 colour of acai fomhen fg} *36 a tappeats ony inthe colour of basic ormwhen TT 5 ‘The pH range of indicator is : (A) 37-69 (8) 4.0-66 (©) 40-69 (0)3.7-68 © 2,8 _lonisation constant of each HA (weak acid) and BOH (weak base) are 3.0 x 10 each at: 298K. The percentage degree of hydrolysis of BA at the dilution of 10L is: (a)25 (8) 50 (©) 75 (0) 40 2.9 Which ofthe folowing concentrations of NH," will be sufficiént to prevent the precipitation of Ma(OH), from a solution which is 0.01 M MgCl, and 0.1 M NH (aq). Given that : Kep of Mg (OH). 2.5 x 10" and Ky for NH,(aq) =2 «10-8, (a)o.o1m (8).0.02M ()0.001m (0) 0.04m ing which pair of cation and anion 240° pOH =7~0.5 pk, + 0.5 pK, is true for aqueous solution cont (A) GyH,NH,", CH,COO- (8) NH, F° (C) Both (A) and (B) (D) None of these 2414 An acid-base indicator which is a weak acid has a pK, value = 6.35. At what concentration ratio of sodium acetate to acetic acid would the indicator show a colour half-way between those of its acid and conjugate base forms? pk, of acetic acid = 4.76. og 2 = 0.3] ~ ea 7st (5:4 (oy2z4 BNBescnepce10 Qhemistry 242 2.43 244 2.45 2.16 2a7 IEE (Advanced) RRB ‘The indicator constant of phenolphthalein is approximately 10. A solution is prepared by adding 100.01 c.c. of 0:04.N sodium hydroxide to 100.00 c.c. of 0.01N hydrochloric acid. If a few drops of phenolphthalein are now added, what fraction of the indicator is converted to its coloured form? 4 3 4 9 “3 @F Oz OF A certain mixture of HCI and CH,~COOH is 0.1 M in each of the acids. 20 mi of this solution is titrated against 0.1M NaOH. By how many units does the pH change from the start to the stage when the HCl is almost completely neutralised” K, for acetic acid = 1.8 x 10° (A) 2.03, _ + @)0775 (©) 2.325 (0) 3.172 ‘buffer solution is made by mixing a weak acid HA (K, = 10-) with its salt NaA in equal amounts. What should be the amount of acid or salt that should be added to make 90 mlof butter solution of buffer capacity 01? (A) 10 mmoles (8) 22 mmoles (C)Smmoles (0) 1 mmoles ‘A sample of water has a hardness expressed as 80 ppm of Ca. This sample is passed through an ion exchange column and the Ca* is replaced by H’, What is the pH of the water after it has been so treated? [Atomic mass of Ca = 40] 3 @)27 (©) 54 (0) 24 ‘Toa 100 mL of 0.1 M weak acid HA solution, 22.5 mL of 0.2 M solution of NaOH are added. Now, what ‘volume of 0.1M NaOH solution be added into above solution, so that pH of fesulting solution be 4.7 [Given : (K(A") = 5 * 10°) (a) 5mt, (8) 20 mL (©) 10 mt (0) 15 mt (@) When 100miof0.1 MNaCN solutions ttrated with 0.1 M HC! solution the variation of pH of solution with volume of HCladded willbe: eat volume of HCl added {b) Variation of degree of dissociation a with concentration for a weak electrolyte at a particular temperature is best represented by (©) 0.4 Macetc acid solution is trated against 0.1 M NaOH solution. The difference in pH between 4H4 and 3/4 stages of neutralization of acid willbe 2 og 3. SECTION - Il: MULTIPLE CORRECT ANSWER TYPE, 248 249 Resonence. IN: A litre solution of pH = 1 diluted upto 10 times. What volume of 2 solution with pH = 2s to be added in diluted solution so that final pH remains "2 (A) 1 litre (8) 10 litre” (€) 100 fire (0) 25 fire The solubility of 2 sparingly solubie salt A, 8, in water at 25°C 1.4 x 10-4 M. The solubility product is 4.1 * 10". The possibilities are (x= ty=2 (8)9: Chemistry ce JBE (Advanced) “RRB ca 220 The variation of pH during the titration of 0.5 N Na,CO, with 0.5 N HCIis shown in the given graph. The following table.indicates the colour and pH ranges of different indicators : a W020 30 40 50 60 v0) of HCI imi) Based on the graph and the table, which of the following statements are true ? (A) The first equivalence point can be detected by cresolphthalein (8) The complete neutralisation can be detected by bromothymal blue. (C) The second equivalence point can be detected by bromocresol red (0) The volume of HCI required for the first equivalence point is half the volume of HCI required to reach upto second equivalence point. 2.21 Select the correct statements (A) pl of NaHCO, solution can be given by (8) AP" ion is amphoteric (C) K,, values of metal nitrates are very-very high (D) Na’ (aq). is conjugate acid of NaOH (aq), PK 1,605 + PKncos z 2.22 Butter solution A of a weak monoprotic acid and its sodium salt in the concentration ratio x : y has = (pH), Buffer solution B of the same acid and its sodium salt in the’ concentration ratio y : x has pH = (pH), If (pH),— (PH), = 1 unit and (pH), + (pH), = 9.5 units, then =3182 (ok, (A)pK= ‘SECTION - Ill : ASSERTION AND REASON TYPE — = 2.23 Statement-4 : Phenolphthalein can be used as an indicator in the titration of weak acid with NaOH, ‘Statement-2 : Near the end point in the titration of weak acid with NaOH, the pH of the solution is alkaline due to hydrolysis of anion (A) Statement-tis true, Stalement-2 i true; Saterient-2 is the correct explanation of Statement (8) Statement-tis tue, Stalement-2 is true; Statement-2 is not the correct explanation of Statement-1 {C) Statement-1 is false, Statement-2 is true. (0) Statement is true, Statement-2 is false. 2.24 Statement-t :Itis difficult to distinguish the strengths of the strong acids such as HCl, H,SO,, HNO}, HBr, HI or HCIQ; in dilute aqueous solutions, Statement.2 : In dilute aqueous solution all strong acids donate a proton to water and are essentially 100% ionised to produce a solution containing H,0" ions plus the anions of strong acid. (@)Statement-t is True, Staternent-2 is True; Statement-2 is @ correct explanation for Statement-1. (8) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1 (C) Statement-t is True, Statemient-2is False , (0) Statement-1 is False, Statement-2is True 75 6) i ad ©) I$9 CREM 8 nes) JEL (Advance) - RRB 2.28 Statoment-1 : 0.20 M solution of NaCN is more basic than 0.20 M solution of NaF. Statement-2 : 0.20™ solution of NaCN is more basic than 0.20 M solution of GH,COONa, {A) Statement-1is Trué, Staterment-2 is True; Staternent-2 Is @ correct explanation for Statement-1 (8) Statement-1 is True, Statement-2 is True; Statement-2is NOT a correct explanation for Statement-1 (C) Statement-1is True, Statement-2is False (0) Statement-1is False, Statement-2 is True 2.26 Statement-1 : A substance that can either act as an acid or a base is called ampholyte. Statement-2 : Bisulphide ion (HS-) and bicarbonate fon (HCO,") are ampholytes. (A) Statement-1 is Te, Stateent-2 is True; Statement-2is a correct explanation for Statement-t (8) Statement-t is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement {C)Statement-t is True, Statement-2 is False (0) Statement-1is False, Statement-2is True ‘SECTION - IV : COMPREHENSION TYPE Comprehension # 1 Consider a solution of CH,COONH, which is a salt of weak acid & weak base. ‘The equilibrium involved inthe solutions are CH,COO- + H,0 == CH,COOH + OH (1) NH;+H,0 === NHOH +H 2) fr+ on = 3H,0 3h If we add these three reactions, then the net reaction is (CH,COO- + NH," + HO ——* CH,COOH + NH,OH 44) Both CH,COO™ and NH,” get hydrolysed independently and their hydrolysis depends on (their initial concentration Ky Ko (the value of K whichis 5@% for CH,COO- and 5 for NH Since both of the ions were produced from the same salt, their inital concentrations are same, Therefore Ky Ky unless & until the value of {c* and “or K, and K, is same, the degree of hydrolysis of ion can't be same. ‘To explain why we assume that degree of hydrolysis of cation and anion is same, we need now to look atthe third reaction ie, combination of H* and OH" ions. Itis obvious that this reaction happens only because one reaction produced H* ion and the other produced OH ions. We can also note that this reaction causes both the hydrolysis reaction to occur more since their product ions are. being.consumed. Keep this thing in mind thatthe equilibrium which has smaller value of equllbrium constants affected more by the common ion effect. For the same reason if for any reason a reaction is made to occur toa greater extent by the comsumption of any one ofthe product on, the reaction with the smaller value of equilibrium constant tends to getatfected mare. Therefore we conclude thet firstly the hydrolysis of both the fons occurs moré in the presence of each other (Cue to consumption of the praduct ions) than in each other is absence. Secondly the hydrolysis ofthe ion hich occurs to a lesser extent (due to smaller value of K,) is affected more than the one whose K, is. ‘greater. Hence we can see that the degree of hydrolysis of bth the ions would be close to each other when they are getting hydrolysed in the presence of each other. 2.27 Inthe hydrolysis of salt of weak acid & weak base (A) degree of hydrolysis of cation and anionis diferent {@) degree of hydrolysis of cation and anion Is same {©) degree of hydrlysis of cation and anions different and they can never be assumed same. (©) degree ofhyartysis of cation and anions diferent buthey are vey cose to eachother wen they are getting hydrolysed in the presence of each other. UNSesenence —— albo ' Chemistry ca IEE (Advance) - RRB ca 228 For 0.1 MCH,COONH, salt solution given, K, = Kinwor 72" 10%. In this case : degree of hydrolysis of cation and anion is (A) exactly same (B) slightly different (C)can'tsay (D) different but can be take approximatly same 228. inasoutonefNeHCO,, the amphi avon can undergo ination to form ion and hydro} form Otten Heo, + H,0 <2 co +H, Heo, +H,0 2[AKOH),(H,0),}8) + 3H,S(9) More stronger base can remove 4H" ons as follows 1AUH,0),P* + 40H” == [AI(OH),(H,0)] (aq) + 4H,0(0) 230 Which of [A\(H,0),)", H,S or H,O isthe strongest acid ? (A)TAKH,O)P” (AHS (CyH,0 (D)all same 2.31 Abase which will behave just like S*: (aco (8) CH,OH (O)NH, Qn 2.32 Another ion that would behave similar to A (aq) in forming an acidic solution is (A) Bega (8) Bagi, (Nar (Tr 233. [A(OH), (H,0),](s) more simply written as AKOH),(s)is (A) acidic (8) basic (C)neutrat (O)amphoteric > 234 Which gas would get absorbed when passed into a solution of AI (aq) ? (A)NH, (8) NO (co (0)0, SECTION - V : MATRIX - MATCH TYPE, 238 Match the following It kof HCN = § x 10", k,of HOCN = 3.2 10, k, of NH, = 1.8 « 10+ k, of CH,COOH = 1.8% 104 (alldata at25°C) ~ Column Column-l (pH at 25°C) (A) 102M Nacn ()pH>7 (8) 100 ml of 10 MNaCI+ 100 mi of (pH #7 10°' M HCI + 300 ml of 10-* M NaOH {C) 10" MHCI +10" HCN (opH<7 (0) 10" MNH,ocN ()pH=7 - ()pOH<7 DN Sescvence — — ———______________y5 Chemisiry JEE (Advanced) -RRB ca 236 Columns! Column-tt (A). NaHCO, (aq) (p) Significant cationic hygrot (8) CH,COONH, (ea) (@) Significant anionic hydrolysis (© | KS0,AYSO),24H,0(q) (Acidic (pH <7) ©)” NacN faq) (5) Basic (pH > 7) (t) pH is independent of concentration 237 (Use log 1.8 = 0.26, k, of formic acid = 1.8 x 10, k, of acetic acid = 1.8 x 10°, k, of ammonia =1.8X 10+, k, Of H,S= 107 and k,, of H,S= 10 for the following matchings) Match the entries 6f column I! for which the equality or inequality given in the column (are satisfied Column | Column I (A) 10 M HCI solution > 0.1 MH,S solution _(p) a, (degree.of dissociation of water) (8)CH,COOH solution atpH equalto4.74 ——(q) [OH] = NH,OH solution at pH equal to 9.26 (€)0.1 MCH,COOH solution (1). (degree of dissociation of electrolytes) 0M HCOOH solution (0) 0.1 Mofaweak acid HA,(k, = 10") solution (s) pH : <0.01 M of a weak acid HA,(k, = 10) 1 solution © [] SECTION - VI: INTEGER TYPE 2.38 ‘The equilibrium constants for amino acids are given in terms of succesive ionization constants of the protonated form. For example, equilibrium constants for Glycine (NH,CH,COOH) are K,, = 5 10> M and K,,=2 * 10-1 M. What will be the pHat the Isoelectric point for this amino acid and pH of 0.02 M protonated Giycine in pure water respectively [Take log 2 = 0.30] 2.39 When NaOH solution is gradually added tothe solution of a weak acid (HA), the pH of the solution is found tobe 5.0 atthe addition of 10.0 mL of NaOH and 6.0 a the further addition of 10.0 mL 6f Sime NBOH. (Total volume of NaOH = 20 mL) calculate pk, for HA flog 2 = 0.3] [Fill your answer in the form of multiple of 10-* for example if your answer is 2.1 then fil21 as your answer} 2.40 Calculate the hydrogen ion concentration (in mol/ém?) in a solution containing 0.04 mole of aceticacid and 0.05 mole of sodium acetate in 500 mi. of solution. Dissociation constant for acetic acids 1.75 x 10° Report your answer after multiplying by 2* 10 DN 8esenense— $________________ Jar‘Chemistry 02 TOPIC 3 SECTION -1: STRAIGHT OBJECTIVE TYPE 34 ‘The vapour pressure of the solution of two liquids A(p? = when x,= 0.4. The result shows that (A) solution exhibits ideal behaviour. id (@) solution shows positive deviation. (C) solution shows negative deviation. (0) soluton wil show positive deviation for lower concentration and negative deviation for higher concentrations. 2) JEE (Advanced) RRB ca SOLUTION & COLLIGATIVE PROPERTIES 30 mm) and B(p*= 120 mm) is found to be 100 meh 3.2 Barium ions, CN and Co* form an ionic complex. If this complex is 75% ionised in aqueous solution with \Vant Hoff factor) equal to four and paramagnetic momentis found to be 1.73 BM (due to spin only) then the hybridisation state of Co (Il) in the complex will be alse ees" (C)spe (D) dsp" 3.3 Osmotic pressure [in atm] of a 0.1 M solution of K,[Fe(CN),, which undergoes 50% dissociation, will be at27°C ars (@)3.69 (C)4059 (0) none of these 3.4 Inan ideal mixture of liquids Aand B the mole fraction of Ais 0.25. If the ratio of P,°to P,?is 7/3, how many repeated distilations would be required as a “minimum” to obtain a small quantity of distilate which has a mole fractionofA, better than 0.807 as @z (3 5 3.5 The molar heat of vapourization of toluene is AH, fits vapour pressure at 315 Kis 60 torr & that at 355 Kis 300torrthen aH=? (log 2= 0.3) (A) 37.5 kaimole (@)3.75 kslmole (©)37.5.dimot (0)3.75 simole 3.6 Which of the following has been arranged in order of decreasing freezing point? (A) 0.05 M KNO, > 0.04 M CaCl, > 0,140 M sugar > 0.075 M CuSO, (€) 0.04 M BaCl, > 0.140 M sucrose > 0.075 M CuSO, > 0.05 M KNO, (C) 0.075 M CuSO, > 0.140 M sucrose > 0.04 M BaCl, > 0.05.M KNO, (0) 0.075 M CuSO, > 0.05 M NaNO, >0.140M sucrose >0:04MBaCl, > 3.7 Asolution of xmnoles of sucrose in 100 grams of water freezes at -0.2°C. As ice separates the freezing point goes down to0.25°C. How many grams of ice would have separated? (A) 18 grams (8) 20 grams (C}26 grams (0)23 grams 3.8 A sample of airis saturated with benzene (vapour pressure = 100 mm Hg at 298 K) at 288K, 750mm Hg pressure. Ifitis isothermally compressed to one third ofits intial volume, the final pressure of the system is. (A) 2250 torr (8) 2180 torr (C)2050tor (©) 1950 torr 3.9 Available solutions are 1L of 0.1 M NaCI and 2 of 0.2'M CaCl. Using only these two solutions what ‘maximum volume of 2 solution can be prepared having [CI] = 0.34 M exactly. Both electrolytes are strong (ay25e (824 (23 (D)None ofthese 3.40 Calculate the osmotic pressure of the solution prepared in the above question (3.12) T = 300 K, (R=0.082 L atm mol"K~!) (A) 10.8atm (8)12.8.atm (0)5.6atm (D)None of these$0, Cher ty, 8 ie, SBE (Advanced) RRB ca 3:11. Consider equimolal aqueous solutions of NaHSO, and NaCl with AT, and AT, as their respective boing ay point elevations. The'value of yo) yy willbe: at (15 3s oe 3.42 Asolute’S' undergoes a reversible trimerization when dissolved in a certain solvent. The boiling point elevation of its 0.1 molal solution was found to be identical to the boiling point elevation in case of a 0.08 molal solution of a solute which neither undergoes association nor dissociation. To what percent had the solute ‘S' undergone trimerization? (A) 30% (8) 40% (€)50% (0)60%. 3.43. For @ solution of 0.849 g of mercurous chloride in'50 g of HgCl,(é) the freezing point depression is. 1.24°C. K, for HgCl, is 34.3. What is the state of mercurous chloride in HgCl, ? (Hg ~ 200, Cl- 35.5) (A)as Hg,Cl, molecules (B) as HgCi molecules (C)as Hg" and Cl-ions (0)as Hg," and Cr ions 3.14 Consider the following statements and arrange in the order of truoffalse as given in the codes. , : Vapour pressure is acoligative propery, SS, : Freezing point ofa solution is always lower than that of the pure solvent. 8, : Acetic acid undergoes association in benzene. The moiar mass of acetic acid, determined by elevation cof boiling pointis always higher than its normal molar mass. S, : Osmotic pressure measurements can be used for determination of molar mass of polymers. (AFFFF (@FTT (om (O)TFTF SECTION - Il : MULTIPLE CORRECT ANSWER TYPE 3.18 _ Dryairis siowiy passed through three solutions of different concentrations, ¢,,c, and ¢, ; each containing (fon voatie) NaC! as solute and water as solvent, as shown in the Fi. ifthe vessel 2 gains weight andthe vessel 3 loses weight, then > (A)e,>0, ®)o,<0, ()e,<0, (D) o> 6 3.16 Vapour pressure of solution containing 6g ofa non-volatile solute in 180.g of water is, is further added vapour pressure increases by 0.02 torr. Which of the folowing is tue ? (A) The molecular weight of solute is $4g mor (B) The vapour pressure of pure water is 20,22 torr (C) Addition of more water inthe solution wil further raise the vapour pressure of solution (0) The vapour pressure of pure water is 22.22 torr 3.17. Twoliquids A and B form an ideal solution. The solution has a vapor pressure of 700 torr at 80°C. Itis distilled {11 2/9" ofthe solution is collected as condensate. The composition of the condensate is x= 0.75 and that ofthe residue is x",= 0.30 Ifthe vapor pressure ofthe residue at 80°C is 600 Tor, which ofthe folowing is! aretrue? > (A) The composition ofthe orginal quid was x, {) The composition ofthe orginal quid was x, 0 (02 2 Ton, (0)P,°= 500 Tor: US 22sen20¢e —__—_—_____________0 ' Chemistry a “19 JBE (Advanced) - RRB ca SECTION - Il : ASSERTION AND REASON TYPE 348 ‘Statement-2 : No two substances can have exactly the same nature of intermolecular forces & also of the same magnitude, (A) Statement-t is True, Statement-2is True; Statement-2 is a correct explanation for Statement-1. (8) Statement-t is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Staternent-1 (C) Statement-1 is True, Statement-2 is False (0) Statement-+ is False, Staternent-2 is True 3.19 Statement-1: When a cals placed in hypertonic solution it hnks. ‘Statement-2 : Reverse osmosis is used for désalination of water. (A) Statement: is True, Statement? s Tue; Statement2 is acorect explanation for Statement- (B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1 (C) Statement-1 is True, Statement-2 is False (0) Statement- is False, Stalement2s True 3.20. Statement-t : The difference in the boiling points of equimolar solution of HCl and HF decreases as their molarity is'\decreased. Statement-2: The extent of dissociation decreases steadily with increasing dilution (A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1. (@)Statement-1 is Trve, Statement-2is True; Statement-2 is NOT a correct explanation for Siatement-1 (C) Statement-1 is True, Statement-2 is False (0) Statement-is False, Statement-2is True 3.21. Statement-t°: When ‘a’ mL. of a 0.1 molal urea solution is mixed with another ‘b’ mL of 0.1 mola! glucose solution, the boiling point ofthe solution is no different from the bolling points of the samples. Prior to mixing but if'a! mL of 0.1 molal urea is mixed with ‘b’ mL of 0.1 motal HF, the boiling point of the ‘mixture is different from the bolling points of the separate samples Statement-2 : HF is an electrolyte (weak) whereas glucose is a non electrolyte. (A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1 (B) Statement-t is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1 (C) Statement- is True, Statement-2 is False (0) Statement-1 is False, Statement-2 is True SECTION - IV : COMPREHENSION TYPE, Comprehension #1 IDEAL SOLUTIONAT FIXED TEMPERATURE Consider two liquids 8 and'C’ that form an ideal solution. We hold the temperature fied at some value T that is above the freezing points of B' and C’. We shal plot the system's pressure P against x, the overall mole fraction of B in the system Past ng eng ; Mot Ag +ng + ng + ng Where nf and ni are the number of moles Bin the liquid and vapor phases, respectively. Fora closed system x, is fixed, although ng and ni may vary. Letthe system be enclosed in a cylinder fited with a piston and immersed in a constant-temperature bath. To see what the P-versus-x, phase diagram looks lke, let us initially set the extemal pressure on the piston high enough forthe system fo be entirely Iquid (point Ain figure) As the pressure is lowered below that at, “the system eventually reaches a pressure where the liquid just begins to vaporizes (point D). At point D, the liquid has composition xf where xf, at Dis equal to the overall mole fraction x, since only an infinitesimal ‘amount of liquid has vapourized. What is the composition of the first vapour that comes off ? Raout's law, P= XSP~ relates the vapour-phase mole fractions to the liquid composition as flows xy = RE 4) IN Gesenence ——{5 Cem) 4s FEE (Advanced) -RRB Where Pf and P2.are the vapour pressures of pure'B' and pure 'C’ at T, where the system's pressure P ng ; ‘equals the sum P, + P, of the partial pressures, where xf = Tar} 1 end the vapor is assumed ideal Ag(Only liquid) Df (First vapor appears) F4 (Last liquid vaporizes)} o x 4 eee (Mole ton of) BPE easton ee 2) Let B be the more volatile component, meaning that PS > P£. Above equation then shows that x3/x% > xg xf. The vepor above an ideal solution is richer than the liquid inthe more volatile component. Equations (1) and (2) apply at any pressure where liquid —vapor equilibrium exists, not just at point D. Now let us isothermally lower the pressure below point D, causing more liquid to vaporize. Eventually, we ‘teach point Fin figure , where the last drop of liquid vaporizes. Below F, we have only vapor. For any pointon the line between D and F liquid and vapor phases coexist in equilibrium, 3.22 If the above process is repeated for all other compositions of mixture of C and B. If all the points where vapours start convering nto iquld are connected and ale points where vapours got completly converted ito aud are connect Then obtained graph wil ook ike te t liquid (2) Jp, P ©) ® anour(o) ®) “O Mole fraction of B 1 0 Mole fraction of B 4 t I , te jad 7 P oar P ti P, Ey rigid Ss co? v) © E apait lees) (0 Mole fraction of B “Mole fraction of B 4 3.23 The equation of the curve obtained by connecting all those points where the vapors of above mixture (all matures of diferent composition are taken just stat forming wil be WP =Pt, + (PPL), (Pers (PX, Pare ie (OP BPE -PB)-PB (P= X58 -Pa)+P PN Besenence =£2 Cher, i SEE Advance) RRB 3.24 Twoliquids Aand B form a non ideal solution which obey the equation P,=P*, +P", — P°,) xq + 2(P*, ~ P*,)x,? When equimolar mixture of Aand B is distiled find the composition (by mole) when this mixture will have a single boing point. (Pe, > P*,) where P*, and P°, are vapour pressures of pure And B respectively X, = mole fraction of Bin quid phase (A3:1 (B)2:3 (o)4:2 (D) 1:3 Comperhension #2 The pressure of two pure liquid A afd B which form an ideal solutions are 400, mm Hg atid 600 mm Hg respectively at temperature T. A quid containing 3 : 1 molar composition pressure can be varied. The solutions slowly vaporized at ternperature T by decreasing the applied pressure staring with a pressure of 760 mmig. Apressure gauge (in mm) Hg is connected which given the reading of pressure applied 3.25 Thereading of pressure Gauge at which only liquid phase exists. (Aas (8)399 (299 (O)None 3.26 The reading of pressure Gauge at bubble point is (a) 500 (e)600 (700 (O)None. 327 The readingof pressure Gauge at which only vapour phase exists is, : (a)50t (8487.14 (€)425 (0)526 ‘Comprehension #3 Colligative property measurementis one of the techniques ued in the measurement chemical quantities with reasonable accuracy. if 40.65 gm sample of K,S0, and BaSO, is dissolved in 900 gm of pure water to form a solution A’ at 57°C, its vapour pressure is found to be 39.6 torr while vapour pressure of pure water at 57°C is 40 torr. Density of solution Als 1.24 g/ml Ina diferent experiment when small amount of pure BaSO, is mixed with water at 57°C it gives the osmotic rise of 4.05 x 10° atm, (R= 0.082 Lt-atm/mol-K ; K = 39, Ba = 137, S= 32, 0 = 16) 3.28 Percentage of K,SO, in the sample is: (A) 65.75%, ()72% (c)60.25% (0)78:74% 3.29 Solubilly product of BaSO, in water at 57°C is (a)sx to" (8)3.125x 10" (C)5.625%10-> (0)2.25x10- 3.30 Concentration of B= fons in solution A’ is (A)3.5 x 10-* M(B) 4.7 x 10° M(C) 2.5.x 10° M(D) 4x 10M 3.31. Elevation in boling point of solution Ais (K, water = 0.54 K-kg/mol) : (A)0.3K (B)O.1K (C)0.04K (0) 0.05 K SECTION - V : MATRIX - MATCH TYPE 332 Columal Column i (A)Acetone + CHCl, (p) 4S, > 0 (B) Ethanol + Water (@avn>0 (OGHBr+C.Hy. (ati <0 (D) Acetone + Benzene (s) Maximum boiling azeotropes: ()Minintum boiling azeotropes 3.33” Mateh the Column Column Column. (A)0.1 MAL{SO), (0) Soktion with highest boing point. (8)0.1 MAPO, (@) Van' Hoff factor is greater than 1 (0)0.1 Mure. (© Solution with lowest osmotic pressure (0)0.1 MMgcl, (8) Solution with lowest freezing point. IN Resorence —$9 hms $e 88 Advance) RRB SECTION - VI 334 3.35 3.36 337 3.38 3.39 3.40 INTEGER TYPE 2.58g of sulfurin 100g 6f CS, Fas depression in freezing point of 0.01°C.K,= 0.1?molal, Hence, the atomicity of sulfurin CS, is 0.0125 mol of sucrose is dissolved in 100 gm of water and it undergo partial inversion according to following ‘equation = C.,,H,,0,, + HO —> C,H,,0,+ C,H,,0, fon 1 7 If elevation in boiling point of solution is 0.104°C calculate ;f mol percentage of sugar inverted Kiyo ®0.52). 25 mloof FeC,O, dissolved in 186 gm of water calculate depression in freezing point. If 10 ml of same FeC,0, tiated with 30 ml of 0.4 M Kind, inacidic medium (k, for H,O = 1,86, Assume 100% ionisation of FeC,0,) ln 10° Lite sample of hard water CaSO, and MgSO, is present. If elevation in Boiling points 0.000052°C. Calculate the degree of Hardness of hard water. (K, for H,O = 0.52) ‘The vapour pressure offluorobenzene at t°C is glvenby the equation 1250 log p (mm Hg) = 7.0 - gay Calculate the boiling point of the liquid in °C if the external (applied) pressure is 5.26% more than ‘required for normal boiling point. (log 2 = 0.3) 41g of arsenic dissolved in 86 9 of benzene brings dowm the freezing point to §.31 °C from 5.50 °C. IfK, of veramne49 ne aoniyetne macale 8-76) + ‘Assume liquefied petroleum gas (LPG) is a 50-50 (by mole) mixture of n-pentane and n-butane. Calculate the Calorific value (in kl/mo! ) of gas available from a newly filed cylinder, Give your answer divide by 100. n-butane,C,H,. repentane, C.Hy, Vapour pressure 1800 Tort 600 Torr Caloric value 2800 ksimol 3600 ks/mol pgs $$$Chemistry JEE (Advanced) - RRB ca Topic | — CHEMICAL KINETICS 4 & RADIOACTIVITY STRAIGHT OBJECTIVE TYPE SECTION - 44 GF (aq) + BrO,{aq) + GH" (aq) ~» 31, (aq) + Br (ag) + 3H,0(0) ‘These data were obtained when this reaction was studied. Reaction rate 1M} rOsaM | LM | re c.oot0 | 0.0020 | o.010 | “aox 10% ‘o.v20 | 0.0020 | 0.010 | 16x10" 0.0020 0.0040 6.010 46x 10% oat | o.cc40- | 0.020 | 16x10" What are the units of the rate constant for this reaction? as (8) mol L's" (Cy L mor s* (0) L mot? s+. 4.2 Ina hypothetical reaction ‘A(aq) <== 2B(aq) + Claq) (1% order decomposition) "Ris optically active (dextro-rototory) while 'B' and 'C' are optically inactive but ‘B' takes partin a titration reaction (fast reaction) with H,0,, Hence the progress of reaction can be monitored by measuring rotation of plane of polarised light o by measuring volume of HO, consumed in titration, Inan experiment, the optical rotation was found to be 0 = 30” at t = 20 min, and 0 = 1° at t= 50 min. from start of the reaction. ifthe progress would have been monitored by titration method, volume of HO, consumed at t= 30 min. (from start) is 30 ml then volume of HO, consumed at t= 90 min. will be: (A)60 mi (B)45 mi (C) 52.5 mi (0) 90 mi 4.3 Atacertain temperature, the first order rate constant k, is found to be smaller than the second order rate constant ,, Ifthe energy of activation E, ofthe first order reaction is greater than energy of activation E, ofthe second order reaction, then with increase in temperature. (A)k, willincresise faster than k,, but ahways wil remain less than k, (8) k, wil increase faster than k, (©)K,wilincrease faster than k, and becomes equal to k, (©)K, wil increase faster k, and becomes greater than k, yr 8 44 AO, ‘All reactions are of Ist order. tac 5k SS 50 Attime t= t,t, >) (8) Toy 7%: Therefore at > io fie t=, (where >t) ° 1S we th wn caret Warp @a=6 (yap = 04 (D)a+pao4 especies sgt9 hey 6 sr Rh 4.8 Inthe formation of HBr from H, & Br,, following mechanism is observed. ste (A) Br, ==> 288 Equioium step (6) H, + Bre —> HBr+He © Slowstep (C) He + Br, —> HBr+ Bre Faststep Calculate the rate of reaction, if concentration of hydrogen is twice that of bromine and the rate constant |s equal to one rutherford. Concentration of bromine is 1 M. (A)2* 40 dps (B) 10 « 10° dps (C)20.2% 10% dps (0) 4« 10° dps 4.6 Agraph between log t,,2 and log.a (abscissa), a being the intial concentration of Ain the reaction is given For reaction A -» Product, the rate law is : Karo a4 ~d{A} A) 3p =KIAP 4.7 Inagaseous phase reaction, A(g) —» B(g) + +C(g). The increase in pressure from 100 mm to 110 2 mm is observed in § minute. The rate of disappearance of A, in mm min-*is : (aya (68 (©) 16 (22 4.8 Fora t#order reaction (gaseous) (constant V, T) b aA —-»s(b-1)B + 1.6 (with > a) the pressure of the system rose by 50(2~*} in atime of 10 min ‘The half fe of the reaction is therefore. (A) 10 min (8) 20 min (©) 30min (0) 40 min. 4.9 Fora.certain reaction the variation ofthe rate constant with temperature is given by the equation Ink, =Inky + SP (2 orc) ‘The value of the temperature coefficient of the reaction is: (aot (8) 1.0 (10 (3 4.40 A reaction takes place in three steps ; the respective rate constants are k,, k, and k,.The overall rate Kiks = "Gq If energies of activation are 40, 30 and 20 ki, the overall energy of activation is ‘constant {assumming'A'to be constant for al): (ay 10 B15 ©)30 (0) 60 4.11 Inacettain reaction, 10% of the reactant decomposes in one hour, 20 % in two hours, 30% in three hours ‘and so on, The dimensions of the rate constant is (A) hour (8) mole litte sect (C) litre mole-' sect (D) mole sec?5 flemtsny “412 413 4a4 445 4a7 4.18 JEE (Advanced) + RRB ca ‘Some graph are sketched for the reaction A» B (assuming different orders). Where ‘a’ represent the degree of dissociation (a) ia) 1 -(b) fo] (©) ma (: > "> > to ‘The order of reaction are respectively. (04,2 B)1,0,2 (02,01 1.2.0 ‘Compounds And B react with a common reagent with frst order kinetics in both cases. If 99% of A must react before 1% of B has reacted, what is the minimum ratio for their respective rate constants? (ay 916 (8) 229 (c) 500 (0) 458, The activity per ml of a solution of radioactive substance is x. How much water be added to 200 mi of this solution so that the acitivity falls to x20 per ml after 4 half-lives ? (A) 100 mi (8) 150 mi (C) 80 mi (0) 50 mi ‘A eaction with respect to X is zero order til the concentration is reduced to half of intial concentration. Then the reaction become first order with respect tot if the value of rate constants forthe zero order and first order are equal tok (in magnitude), then find the time taken to reduce the concentration of X to + th of ts original concentration k, +, 3ena X , 3un2 42 4, dena ange ae ae ee Wat OR Ox Oxy For the decomposition of H,0,(aq) itwas found that Vo, (t= 1 min.) was 100ml (atO°C and 1 atm) while Vo, (maximum) was 200 mL (at 0% and 2 atm). If the same reaction had been followed by the titration ASI! (¢= 0) had been 40 mL, what would VIM, (t= 15min) have been ? (4)30 mL (@)25mL ()20m. (018m method and if VM ( ‘Areaction can take place by two paths. k, and k, are rate constants for the two paths & E, and E,are their respective activation energies. AttemperatureT,: ky > ke, Ey < Ey. if temperature is raised to T,, the rate constants change tk,” & ka’. Which relation if Gorreét between k,, yy Ky’ & ky’ (considering activation energy does not change with temperature). Ke ee Fru Oi @ yk Consider the following statements and arrange in the order of true/false as given in the codes. A 5; The rate ofthe reaction A» B having the rate taw ~ 4) - 4 fa (6] when plotes against time wit exhibit a maximum at some time, 'S, :A catalyst in @ chemical reaction increases the forward , and decreases the backward E, Sy :Acataiystin a chemical reaction decreases both forward and backward E, Fora first-order reaction, the time required to reduce successively the concentration of reactant by a constant fraction is always same. A amr (8) FFFF (FTF Tr UN Sescvence —_____________2 Chemistry JEE (Advanced) - RRB ca SECTION - Il : MULTIPLE CORRECT ANSWER TYPE 419 4.20 421 422 4.23 For the'consecutive reaction ate) 5 alte) ,¢ folowing curves were obtained depending upon the relative values of ky & ky « c 2 = ¢ 8 8 “A A 8 Tie Time Figure 1 Figure 2 Now which of he following is the correct match ? (A) figure 4 = (ky < ky) (8) figure 2 —(k, > k,) (©) figure 1 ~ (k, >> k,) Which is correct graph A) bun] \ See. order ® of $e) Est order a (rilial concentration) tre ae) \ Ae gaen.cone Lea Jc | ist order oy oo $9) and order ©) | ‘hemp. ‘ (Initial concentration) For a certain reaction A ——» products, the t,, as a function of [Alp is given as below Alo (M) 01 0.025 ty, (min): 100 §0 Which of the folowing is true : (A) The order is 3 (B) typ would be 100Y70min for [Aly = 1M (C) The order is 1 (©) tyz would be 400 min for [Alp = 1 M ae Forth actin 24 +8 —+ Cw erate aw 21 A BF a ste th A nd Bin stoichiometric proportion. Which is/are true ? (A) unit of kis Ms (8) [A}, [8] and {C] all willbe linear functions of time. (©) IC] = 2kt (O)[C]=kt ‘The reaction 2NO + Br, —> 2NOBr follows the mechanism : (1) NO+ Br, Ease NoBr, (2) NoBr, + NO —SlOW_, 2NoBr Which of the folowing isare true regarding tis : (A) The order of the reaction with respect to NO is two. (8) The molecularty ofthe steps (1) and (2) are two each, (C) The molecular ofthe overall reaction is three. “ (©) The overall order of the reaction is three.25h) Ct a IEE (Advanced) = RRB 424 Thepolarimeterreadings in an experiment to measure the rate of inversion of cane suger (Istorder reaction) were as follows time (min) 0 0 @ angle (degree): 902018 Identify the true statement (s)? [log 2= 0.3, log (A) The half ite ofthe reaction is 75 min (8) The solution is optically inactive at 120 min. (C) The equimolar mixture of the products is dextrorotatory (0) The angle would be 7.5” at haf ime 4.25 Identify the true statement(s) (A) A catalyst is chemically unchanged at the end of a reaction (8) Acatalyst may appear in the kinetic rate equation of the reactions {C) Acatalyst will not affect the composition of an equilibrium mixture (©) A catalyst cannot cause a non-spontaneous (AG > 0} reaction to proceed 48, log 7 = 0.84 , log, 10 4.26 The half-period T for the decomposition of ammonia on tungsten wire, was measured for different intial pressures P of ammonia at 25°C. Then P (mm tig) 1 21 4873120 T (sec) 48 92-210 320525 (A) Zero order reaction (B) First order reaction (C) rate constant for reaction is 0.114 mol lt~* sec’ (0) rate constant for reaction is 1.14 seconds. 4.27 The substance undergoes first order decomposition. The decomposition folows two parallel frst order reactions as ee ASA Kin 10 sect and K, = 4 10° sec Be Ifthe corresponding activation energies of parallel reaction are 100 and 120 kJ mot” then the net activation energy of Ais / are : (A) 1204S mor" (8) 116 KI mot (C) 100 KI mot (D) 150 KJ mor* Ci] = (1) kt where 428 A certain reaction obeys the rate equation (in the integrated form) [C*\~ C, is the intial concentration and C is the concentration after time, t. Then (A) the unit of k for n = 1 is soc" (8) the unit ofk for n = 2 is litre mor-* sec"! (C) the unit of kforn = 3 is:mol tre sec" __(D) the unt of k for n = 3 is litre? mot sec" 4.29 Acertain reaction A -> B follows the given concentration (Molarity)-time graph. Which of the following statement(s) is/are true ? : os , a [as wae a © 20 40 60 80 100 Time (sec) —+ (A) The reaction is second order with respect to A () The rate for this reaction at 20 second will be 7 * 10° M s** (C) The rate for this reaction at 80 second will be 1.75 «10 M s-* (©) The [8] willbe 0.35 M at t= 60 second F MN S2senence ay5 Chemisiry 430 Consider the following case of competing 1* order reactions. TEE (Advanced) - RRB. ca Alter the start of the reaction at t= O with only A, the [C] is equal to the {D] at all times. The time in which all three concentrations will be equal is given by : am ‘Where n, = number of moles of B formed and C, is correct. ;oncentration of B then which ofthe following relation dy , Gy av et eG iif volume Vis not constant) Mp (8), = SS (I volume Vis constant) La Sev Be Gp if volume Vis not constant) dy, Co WV “Sy (if volume V is not constant) SECTION - Ill: ASSERTION AND REASON TYPE 432 Statement-t : If the activation energy of reaction is zero temperature, will have no effect on the rate constant. ‘Statement-2 : Lower the activation energy faster is the reaction (A) Statement-1 is True, Statement-2is True; Statement-2is a correct explanation for Statenaent-1 (B) Statement-t is True, Statement-2is True; Statement-2is NOT a correct explanation for Statement-1 (C) Statement-1 is True, Statement-2is False (D) Statement-1 is False, Statement-2 is True 433 Statement-1: For A+ 2B —> C (rate= K{A]"[B)), the half life time of rection is only defined when Concentration of Aand B are in stoichometrc ratio Statement-2 : For above reaction, halflife of reaction is directly proportional o concentration of Aand not to concentration of B due to its zero order. (A) Siatement-1 is True, Statement-2is True; Statement-2is a correct explanation for Statement-4 (@) Satement-t is True, Statement2is True; Statement-2is NOT a correct explanation for Statement-1 (C) Statement. is Tue, Statement-2is False (0) Statement-1is False, Statement 2is True Resonance ————__________________ yfJEE (Advanced) - RRB ca 0" Chemistry a———_—_——— SECTION - IV : COMPREHENSION TYPE Comprehension 4 ‘Study the folowing experiment and answier the questions atthe end of | The following reactions was studied at 25°C in benzene solution containing 0.10 M pyridine CH,OH + (C,H), CCl —> (C,H), . OCH, + HCI A B c ' The following sets of data were observed : ° [Set] Trigal concentration | time difference [Final concentration (¢] fAle_[ [Blo T [atom | a0sm | 25min 3.0085 HE nw _atom | 010M [5 min 0.00391 m | oz0M[atoM | 75min 0.0077 W ato} 4.34 Rates “lin sets 1, and I are respectively (in M min") \ 0 nl (1.30% 10+ 26% 104 1.02 109 ® 0033 0.0039 o.0077 (© 002x104 0.04 « 10 oot7 (0) None ofabove 435 Rate lawofthe above experimentis: (a)r= kA (8) (8)r=K(AP(B] —(C)r=KIAT(BF = (0) r= KIAP IB 4.36 Rateconstantof the above experiment is. (A) 1310 (8) 26* 107 (0) 26 = 10 (0) 1.3 * 10 Comprehension #2 From the following data answer the questions Reaction: A+B —» P alm tem Initial rate M sec™* 300K 400K os 25x10 | dox10 | sox10* | 20% 107 oxo | eoxios | 40%10° 1.0 10° 6.0.x 10% 1.6% 10% 437° The order want Ais: at (a2 (cs )-1 4,38 The valve of rate constant at 300 K is (M? sect): (A)2.667 «10° (8) 2.867 « 10° (C) 2.687 x 108 (0)2.667 x 10 4.39. The energy of activation for reaction (KJ/mol) is (A) 20.83 (8) 13.83 (©) 1823 (0) 10.23,9 Chey es 8 vanced) = RRB Comprehension #3 kB, For a hypotherical elementary reaction A: where ct = 4 mY > 2c k, 2 Initially only 2 moles of A are present. 4.40 The total number of moles of A, B and C at the end of 50% reaction are (a2 3 5 (©) None 441 Number of moles of Bare: (Ay2 (6) 1 (c) 0.666 (0) 0.333 442 The sum of mole of (B) and (C) is: (a2 (e)3 (4 (4 SECTION - V : MATRIX - MATCH TYPE 4.43 ForA+B — C in column Il the graphs given can be from any of these four types. “a (2) Vstime (x axis) (©) t,, VS initial cone. (x axis) (C061 (0 {£221 vetime ans (€) Cone: Vs te ans) Match the grap in Clu forthe gven oder of eacton in Gtimn Couns coun E (A) * order (®) (B) Zero order @ (C) Second order © = (0) Pseudo first order ©) ' % Noe DNSesccence1 Chemie 6 se caance) RRB cn 4,44 Match order of the reaction (in List —1) with the corresponding rate constant (in List— 11) : ListI(order) > List (rate constant) 1 (A)zera . (k= >| ake (8) First @k= + (C)Second (nk= (©) Third (k= 448 Match the following : - Column | Column tt (A) If the activation energy is 65 kJ then how much time (p)o faster a reaction proceed at 25°C than at 0°C. (B) Rate constant of a first - order reaction is 0.0693 min", (qt If we start with 20 mol L-t, itis reduced to 2.5 mol L-* in how many minutes. (C)Half-lives of first-order and zeroth order reactions are same, (930 Ratio of rates at the start of reaction is how many times of 0.693 ? (ifinitial concentration are same for both zero and first order reactions.) (0) The hatte periods are given, (s)14 [A, (0.0677 0.136 0272 (02 ta (ec) 240 480 60 Corder ofthe reaction is. SECTION - VI: INTEGER TYPE 448 it S=kiHPandrate becomes 100 times when pH changes from 2 to 1. Find the order of reaction 4.87 The gas phase decomposition of dimethyl ether follows first order kinetics, ‘CH,OCH,(g) —> CH,(g)+H,(g) + CO(g) 4 “The reactionis carried outin a constant volume container at 600°C and has a half life of 14.6 minute. Initlly oniy dimethyl ether is present at a pressure of 0.40 atmosphre. What is the total pressure of the system after 12 minute ?Assume ideal gas behaviour. (Give your answer by multiplying 100) 448 In the decomposition of H,0, at 300 K, the eneray of activation was found to be 18 kcal/mol while it decreases to 6 kcal/mol wien the decomposition was carried out in the presence of a catalyst at 300 K How many times isthe catalysed reaction faster than uneatalysed one ? (Give your answer by multiplying 10°) 4.49. Decomposition of H,0, (Ist order) 4 H,O,{aq) > H,0(t)+ 50,9) Can be monitored by titration method by pressure measurement. If Time (min) t=0 % © Pressure (mmofHg) 200 375400 ‘While when progress of same reaction was monitored by titration method or the volume of titrant consumed after 10 min was found to be 20 mi. Then complete the following table. Time (min) t=0 10 90 Pressure (mmofHg) 200 (6) (@) ‘Volume of KMnO, @ » @ consumed (mi) IN Sesenence ——____-________yaf© Chemistry JEE (Advanced) - RRB ca TOPIC = 5 SECTION - 1: STRAIGHT OBJECTIVE TYPE STOICHIOMETRY 5.4 15gm Ba(Nn0,), sample containing inert impurity is completely reacting with 100 ml of"11.2 V H,0,, then what willbe the % purty of Ba (MnO), inthe sample ? (Atomic mass Ba = 137, Mn = 55) (A) 5% (B) 10% (C)50% {D)none 5.2 _Inwhat ato shoulda 15% solution of acetic acid be mixed with a3% solution ofthe acd to preparea 10% solution(all percentages are mass/mass percentages) ; ° (A)7:3 (B)5:7 (C)7:5 (0)7:10 5.3 105 mlof pure water at 4°C saturated with NH, Gas, yielded a solution of density 0.9 glml and containing 30% NH, by mass. Find the volume of resulting NH, solution (A) 66.67 mi (8) 16867 mi (C) 133.331 (9)266.67 mi 54 X gramof pure As, is completely oxidised to respective highest oxidation states by 60 ml of 0.1 M hot acidified KMnO, then X, mass of As,S, taken is: (Molar mass of As, S, (ay224g (80226 (C)64.23g 5.5 Volume V, mL of 0:1M K,Cr,0, is needed for complete oxidation of 0.678 9 N;Hg in acigio medium. The volume of 0.3§M KMnO, needed for same oxidation in acidic medium willbe: 2 5 WEY @s% (o113y, (©) can not be determined 5.6 100 mi of 0.1M NaAKOH),CO, is neutralised by 0.25 N HCI to form NaCl, AICI, and CO,. Volume of HCl requiredis (A) 10 mL, (B) 40 mL (©) 100mL. (0) 160 mL. 5.7 100 mL of 0.1N|, oxidizes Na,S,0, in 50 mil solution to Na,S,0,, The normality ofthis hypo solution against KMnO, (which oxidizes it to Na,SO,) would be . ot (02 (10 ote. 58 25ml of 2N HCI, 50 mL of 4N HNO, and x mL of 2M H,SO, are mixture together and-the total volume is made up to 1L after lution. 50 mL ofthis acid mixture completely reacted with 25 mLof a 1N Na,CO, solution, The value of xis (250m (8)62.5 mL. (©) 100 mt, (©) Noneof these 59 An excess of NaOH was added to 100 mL of a ferric chloride solution. This caused the precipitation of 1.428 g of Fe(OH), Caloutate the normality ofthe ferric chloride solution (A)020N | (B}0.50N (C)0.25N (0) 040N 540 0.49 of a polybasic acid H,A (all the hydrogens are acidic) requires 0.5g of NaOH for complete neutralization, The number of replaceable hydrogen atoms in the acid and the molecular weightof'A' would be : (Molecular weight of the acid is 98 gms/mole.) (4) 1,95 (@) 2,94 (©)3,93 (0)4, 92 541A solution of Na, , 0, is standardized iodimetricaly against 0.1262 g of KBrO, . This process requires 45 mL of the Na,S,0, solution. What is the motarity of the Na,S,0,? (@o2m ()0.1M (C)0.05M {O)0.11N DA Sesecence H+$5 "OREO a FEE Advanced) RR 5.12 25.09 of FeSO,.7H,0 was dissolved in water containing dilute H,SO,. and the volume was made up to 4.0 L. 25.0 mL of this solution required 20 mL of an N/10 KMnO, solution for complete oxidation. The percentage of FeSO,-7H,0 in the acidic solution is (A) 78% (b) 98% (c)89% (0)79% 5.13 25 mL of a solution containing HCl and H,SO, required 10 mL of a 1 N NaOH solution for neutralization. 20 mL of the same acid mixture on being treated with an excess of AGNO, gives 0.1435 g of AgCI. The normality of the HCl and the normality of the H,SO, are respectively (A)0.40Nand0.05N (6)0.05Nand035N (C)0.50Nend0.25N _(D)0.40Nand0.5 N 5.14 An queous solution containing 2.14 g KIO, was treated with 100 mi of 0.4 Mi KI solution, the weight of |, producedis- _ 4) 6.096 () (8)7.829 (c) 30.489 (0) 18.2889 5.15 0.70.gof mixture (NH), SO, was boiled with 100 mL of 0.2 N NaOH solution tl all the NH,(a) evolved and get dissolved in solution itself: The remaining solution was diluted to 250 mL. 25 ml. of this solution was neutralized using 10 mL of a 0.1 N H,SO, solution. The percentage purity of the (NH), SO, sample is (ayaa (8)50.8 ()a74 (0)73.8 5.18 A mixed solution of potassium hydroxide and sodium carbonate required 15 ml of an N/20 HCI solution ‘when titrated with phenolphthalein as an indicator. But the same amount ofthe solution when titrated with ‘methyl orange as an indicator required 25 mL of the same acid. The amount of KOH presentin the solution is (A)0.0149 (8) 0.149 (0.028 9 (149 5.17 _ Inaniodometric estimation, the following reaction occur 2Cu + 4» Cu,l,; 1,+2Na,S,0, —» 2Nal+ Na.S,0, 0.12 mole of CuSO, was added to excess of Kl solution and the liberated iodine required 120 mL of hypo. ‘The molarity of typo solution was (ay2 (6)0.20 (ot (0)1.0 548 Consider the following statements and arrange in the order of true/false as given in the codes. S,: The reaction 2H,0, —> 2H,0 + 0, is not an example of a redox reaction 'S_: The equivalent mass of K,Cr,O, in acidic medium is motar mass divided by two. 'S,: The equivalent mass of a substance can be calculated without considering the reaction it undergoes. TFT (8) FTF (C)FFF our SECTION - 1! : MULTIPLE CORRECT ANSWER TYPE , 5.19 Which of the folowing samples of reducing agents is /are chemically equivalent to 26 ml of0.2 NKMnO, to be reduced to Mn** and water. (A) 25 mlof 0.2 MFeSO, to be oxidized to Fe™* (8) 50 miof 0.1 MH,AsO, to be oxidized to HAsO, (C) 25 ml of 0.1 MH,O, to be oxidized to H* and O,, (0) 25 mlof 0.1 MSnCl, to be oxidized to Sn ie 5.20 Fuming H,SO, (oleum)is a homogenous misture of HSO, and SO,, Then which ofthe following statement(s) are correct (A) IfH,S0, and SO, are equimolar in an oleum sample, then strength of oleum is 10.11% (8) If H,SO, and SO, are having equal masses in an oleum sample, then strength of oleum is 11.25% (C) Strength of an oleum sample may be less than 100%. (0) If strength of oleum is (100 + x) %, then x g of water is to be added to 100 g oleum sample to convert whole of SO, toH,SO,, 5.21 1 100 mi of MH,SO, solution is mixed with 100 mi of 88%(wh) H,SO, solution (d= 0.4 grvmi) then (A)concentration of solution remains same _(B) volume of solution become 200ml {C) mass of H,SO, in the solution is 98 gm (D) mass of H,SO, in the solution is 19.6 gm 5.22 Anoleum smaple labelled as 104.5%, for resulting solution. {A) Solution contain 10.09 g H,SO, (8) Solution contain 15.86% free SO, {C) Solution contain 8.49 g H,S0, (0) Solution contain 20% free SO, e§90=0¢—¢—@ pyr 10g of this sample 90 mg water is added then which is/are correct$5, ety SEE Acanced) = RRB CR 6.23 - Which ofthe following contains the same number of molecules? (A) 19 of O,, 2g of SO, (B)Igof CG, ig of NO {C) 112 miof O, at STP, 224 ml of He at 0.§ atm and 273 K (0) 1g of oxygen, 1g of ozone 5.24 A100mImixture of CO and CO, is passed through atube containing red hot charcodl, The volume becomes 1160 ml. The volumes are measured under the same conditions of temperature and pressure. Amongstthe following, select the correct statement(s) ; (A)Mole percent of CO, in the mixture is 60. (B) Mole fraction of CO inthe mixture is 0.40 (C) The mixture contains 40.ml of CO, (0) The mixture contains 40 mi of CO 5.25 0.1 Msolution of KI reacts with excess of H,SO, and and KIO, solutions, according to equation 5+ 10, + 6H" —> 31, + 3H,0 ; which of the folowing statement is correct (A) 200 mi of the Ki solution react with 0,004 mole KIO, (6) 100 mi of the KI solution reacts with 0.006 mole of H.SO, (C)0.5 litre of the KI solution produced 0.005 mole of , { Molecular Weight (D) Equivalent weight of KIO, is equal to | MACE ENE SECTION - Ill : ASSERTION AND REASON TYPE 5.26 Statement-t : In the redox réaction 8 H" (aq) + 41NO," +6 Cl + Sn(s)—> Sac recucing agent is Sn(s). Statement-2 : In balancing half reaction, S,0,*—» S(s), the number of electrons added on the lefts 4 (A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1 (B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1 (©) Statement-1 is True, Statement-2is False (0) Statement-t is False, Statement-2is True 5.27 Statement-1 : Among Br-, 0; , Hand NO, the ons that cannot act as oxidising agents are Br- and H. ‘Statement-2 : Br~ and I’ cannot be reduced > (A) Statement-1 is True, Statoment-2is True; Siatement-2is @ correct explanation for Statement-1. (8) Statement-t is True, Statement-2is True; laternent-2 is NOT a correct explanation for Statement-1 {C)Siatement-tis True, Statement-2 is False (0) Statement-1 is False, Statement.2 is True 5.28 Statement-1 : In the titration of Na,CO, with HCl using methyl orange indicator, the volume required at the equivalence points twice that of the acid required using phenolphthatein indicator. ‘Statement-2 : Two mole of HClare required for the complete neutralization of one mole of Na,COs, (A) Siaterent- is True, Statement-2 is True; Staterient-2 is a correct explanation for Statement-1 (8) Siatement-1 is True, Statement-2s True; Statement-2 is NOT a correct explanation for Statement-1 (C) Statement-t is True, Statement-2 is False ve (0) Statement-1 is False, Statement-2 is True SECTION - IV : COMPREHENSION TYPE, Comprehension #1 ‘We know that balancing of achemical equation is entirely based on law of conservation of mass. However the concept of Principle of Atom Conservation (POAC) can also be related to law of conservation of mass in a chemical reaction. So, POAC can also act as a technique for balancing a chemical equation. For ex- ‘ample, fora reaction ABC, —> AB+C, + 4NO,+4H,0, the 9 a Mt = aa. = Ey, :qumbe (On applying POAC for A, B & C and relating the 3 equations, we get of moles of X) Thus, the coefficients of ABC, , AB & C, in the balanced chemical equation will be 2,2 & 3 respectively and the balanced chemical equation can be represented as 2ABC, —> 2AB + 3C, z Now answer the following questions lesonsnce.0) heb p< ge advanced) RRB 529 5:30 531 ‘Which ofthe following relation is correct regarding the numnerical coefficients p,q,r in the balanced chemical equation pA+qB, —> rA,B, (A)2p=6 (8) q= 1.25p~ (©)r=2q (0) q=0.8p If the weight ratio of C and O, presentis 1 :2.and both of reactants completely consume and form CO and CO, and we will obtain a gasous mixture of CO and CO, What would be the weight ratio of CO and CO, in mixture, (A) 27 (yrs (cy 4:4 (01:2 If the atomic masses of X and Y are 10 & 30 respectivetly, then the mass of XY, formed when 120g of Y, reacts completely with X is Reaction X+¥, XY, (A) 133.3 9 (8) 200 9 & (0) 266.69 (0) 400 g Comprehension #2 5.32 5.33 5.34 Cleum is considered as a solution of SO, in H,SO, , which is obtained By passing SO, in solution of H,SO,, When 100 g sample of oleum is diluted with desired weight of H,O then the total mass of H,SO, obtained after dilution is known as % labeling of oleum. For example, a oleum bottle labelled as "109% H,SO,' means the 109 g total mass of pure H,SO, will be formed when 100 g of oleum is diluted by 9.g of H,O which combines with all the free SO, to form H,SO, as S0,+H,0 —_, H,S0, What is the % of free SO, in an oleum that is labelled as 104.5% H,SO,'? (a) 10 (@)20 (©) 40 (D) None of these If excess water is added into a 100 g bottle sample labelled as "112% H,SO," and is reacted with 5.3.9 'Na,CO, then find the volume of CO, evolved at 1 atm pressure and 300 K temperature after the completion of the reaction : [R= 0.0824 L atm mot K-] H,SO, + Na,CO, —+ Na,SO,+H,0 +O, (A) 2.46.L (8) 246 L (0) 1.23 L (0) 12.3, 1.g of oleum samples diluted with water. The solution required 54 ml of 0.4 N NaOH for complete neutral- ization. The % of free SO, in the sample is (ay 74 (8) 26 (c)20 (D) None of these Comprehension #3 Molality : itis defined as the number of moles of the solute present in 1kg of the solvent. Its denoted by Number of moles of solute Molality (m)=Number of kilo-grams of the solvent Letw, grams ofthe solute of molecular mass ma be presentin w, grams of the solvent, then. Motalty (m) = 75, tae «1000 Relation between mole fraction and Molality : Hand NL a NNen Xq_n_ Moles of solute _ Wa xmg XgN Moles of solvent Wa xmy Xqx1000 _ Wa «1000 _ XexMg We xMa Xai, JASesenense ——____H+— ya$5 Chemisty EE (Advanced) = RRB 535 thera of the mole Faion ofa solutes changed tram + to inthe 800g of solvent then the ratioof ‘molality will be : (aya (3:4 (4:3 1:2 5.36 The mole fraction of the solute in the 12 motal solution of Na,CO, Is: (ayo.822 (6)0.177 (©) 1.77 (0)00177 5:37 What is the quantity-of water that should be added to 16 gm, methanol to make the mole fraction of methanol as 0.25 — (A)27g (8) 12g (C) 18g (0)36g 5.38 A300 gm, 30% (wiv) NAOH solution is mixed with 500 grn 40% (wiw) NaOH solution. What is % (w/v) NaOH. if density of final solution is 2 g/ml. (ayr26 (865 (625 - (None 5.39 What's the motalty of final solution obtained in the above problem (ay1.422 (8) 14.22 ()15.22 (O)None SECTION - V ; MATRIX - MATCH TYPE 8.40 Column Column tr (A) Sa"? + MnO, (acidic) (p)Amount of oxidant available decides the number of 3.5mole 1.2mole electrons transfer (®)H,C,0, + Mn0,- (acide) (q)Amount of reductant available decides the number of B4mole — 3.6mole electrons transfer (08,02 + | (Number of electrons involved per mole of oxidant > 72 mole 3.6 mole Number of electrons involved permole of reductant (O)Fe? + Gr,0;7 (acidic) {s)Number of electrons involved per mole of oxidant < 92 mole 1.6 mole Number of electrons involved per mole of reductant. S41 [H=4,C = 12, 0 = 16, Na=23, P= 31, $= 32] 2 Column ~1 Column — I (A) 4.19 H,S0, (p)200 ml of 0.5 NNaOH is used for complete neutral ization (8)499H,PO, {@)200 mili moles of oxygen atoms (C)4.89 oxalic acid (H,C,0,) (0) Gentral atom has its highest oxidation number (0)5.3gNa,CO, (5) May react with an oxidising agent (t) Shape around central atom is regular. a DNSescnence1 Chemisty @ $88 cAavancer) «RRB ‘5.42 ~ Match the reacting mixture in column | withthe reagent in column Column ~ HC0,+ NaH, (8) NaHPO, + NaNO, (©) FeyS0,),+ FeC,, if (0)Fe0+ Fe,0, 5.43 Match the following : Column | (A)4.5 msolution of CaCO, density 1.45 gm/mi (8) 3M 100 mi H,SO, mixed with 4 M 300 int H,SO, solution {C) 14.5msolution of Ca , (0) in2 litre solution of 4 M NaOH, 40 gir NaOH is added. (€)5m(moial) NaOH solution SECTION - VI: INTEGER TYPE column = (NaOH (@iict {0 Ki20, (8) Zine dust Column th ) mole fraction of solute is 0.2 (q) mass of the solute is 360 gm ('midarty =45 (s) molarity 1.5 (1) 16.66% (whv) of NaOH in solution, 5.84 545 5.48 5.47 5.48 5.48 0.2828 gofiron wire was dissolvedin éxcés dliute H,SO, and the solution was made upto 100 mL. 20mL ofthis solution required 30 mL of N30 K,Cr,0, solution for exact oxidation. Calculate percent purity of Fe inwire. ‘A mixture contains 61.2% BaO, 28% CaO and 10.6% (silica) impurities. What volume in mL of 3.00 MHC! would be required to react completely with 1 g of the mixture ? ‘An oxide of a metal contains 40% oxygen, by weight. What is the equivalent weight of the metal ? ‘A sample consisting of chocolate-brown powder of PbO, is allowed to react with excess of KI and iodine liberated reacted with N,H, in another Goitalner The volume of gas liberated from this Second container at STP was measured out io be 1.12 litre. Find out volume of decimolar NaOH required to dissolve PbO, completely.(Assume all reactions are 100% complete). ‘Give your answer divide by 100. ‘Based on the following Informaion, determine value of xandy : (CH,),AICI, (0.643 g) —> xCH, (g) (0.22 g)+yCt+AP* 49892 5 agct(s) (0.996 g). Umaium is isolated from its ore by dissolving it as UO, (NO,), and separating itas solid UO,(C,0,) xH,0. 1.09 sample of ore on treatment with nitric acid yielded 1.48 g UO,(NO,), which on further treatment with 0.4 g Na,C,O, yielded 1.23 g UO,(C,0,).xH,0. Determine weight percentage of uranium in the original ‘sample and x. Resonence. +aJBE (Advanced) - RRB. ca © Chemiiry TOPIC 6 SECTION -1: STRAIGHT OBJECTIVE TYPE THERMODYNAMICS & THERMOCHEMISTRY 6.1 One mole of an ideal monoatomic gas is caused to go through the cycle shown in igure. Ther the chiange in the internal energy of gas from a to band b to cis respectively =S*.eRT, @)=S>10RT, 62 Consider the folowing data : AH? (N,H,. £) = 50kJlmol, }H® (NH,,g) = ~48 ku/mol, B.E. (N-H) = 393 kJ/mol and B.E. (H-H) = 436 kJ/mol, Ayo H (N Hy £)= 18 kulmot Caleulate the N—N'bond energy in kilmal for N,H, (A) 190 ksimot (8)-100ksImol——_(C) 95 klmol (0)~95 kstmol 6.3 P-V plots for three gases (assuming deal behaviour and similar yz condition) for reversible adiabatic compression are given in the Mi figure below P Plots X, Y and 2 should correspond to respectively (A)CO,, Cl,and Ne (8)SO,,N,O and He Vv (©) He, N, and 0, (0) NH, H,S and ar 6.4 Inthe process shown inthe figure on an ideal diatomic gas, the value of q and AH respectively is : : P. (A) 79.5 PV, and 94.5P,V, (8) 55.5 PV, and 94.5 P,V, (©)12P,V, and o (0)79.5 P\V, and not defined (-- P varies) 6.5 Foran ideal gas having molar mass M, specific heat at constant pressure can be given as? yRM R cM >) otk yt ©) n=O Oyn4 ©) wy 66 —At1000K water vapour at 1atm. has been found to be dissociated into H, and O, to the extent of 3 x 10%. Calculate the free energy decrease of the system, assuming ideal behaviour. (A)-aG= 90,060cal (B)-AG=20cal-—(C)-AG = 480cal_ (0) -AG = DN Sese0e0ce ———__—_——_—__—_—_ 3 45760 cal12 Comic ee caasanced) RRB co 67 _ Inthe reaction COCI,(g) ==> CO{g) + Clg) at 850°C, when the intial pressure of CO & Cl, are 250 and 280 mi af Fig reBhetively: The:equilbrium pressuré is found tobe 380mm of Hg, Calculate the degree of dissociation of COCI, at 1 atm. Whatwill be the extent of dissociation, when N, at a pressure of 0.4 atmis present and the total pressure is 1 atm. (A) 0:32-and no change: (B) 0.32 and 0.4 (©) 0.4 and 0.3 (0) In presenée'ofN, dissociation cannot take place 6.8. When 1 mole of arideal gas at 20 atm pressure and 15 L volume expands such that the final pressure becomes 10 atm and the final volume becomes’60-L.. Calculate entropy change’ for the process (Cy 30.96 J mole" K-") -(A) 80.2 J.'mot* ——(B)62AZKSK'mol* (©) 120 10" Jk*mot* (0) 27.22 Jk" mol* 6.9 During winters, moisture condenses in the form of dew and can be seen on plant leaves and grass. The entropy of the system in such cases decreases as liquids possess lesser disorder as compared to gases, With reference to the second law, which statement is correct, for the above process ? (A) The randomness of the universe decreases (8) The randomness of the surrouridings decreases. (C) Increases randomness of surroundings equals the decrease in randomness of system (0) The increase in randomness of the surroundings is greater as compared to the decrease in randomness. of the system, 6.10 P-Vplots for two gases during an adiabatic process are given in the figure A Pressure ——> ‘Volume ——> . Plot Aand plot B should correspond to : (Assume ideal behaviour) (A)He and O, (8) $0, andar (C) 0, andHe (0) Both (8) and (c) 6.11 Consider the following statements and arrange in the order of true/false as given in the codes. 8, : Change in staté function between two states is a definite quantity and does not depend on path. S, : Intensive properties can't be algebraically added or subtracted. S, : Ratio of two extensive properties result into a parameter that depends on amount of substance. +ySqiMolar heat capacity is a path function The correct order of true / false of the above statements is (AE TRT (B)FFFT (C)TTFT (D)TTTF Wi Sesenence