CAREER INstIruTE| [Pat cs ERCUENGCERESELD ‘Academic Session : 2017-18 JEE (MAIN+ADVANCED) 2019 CHEMISTRY PER coae) Lien => ALLEN” SRGBT-7 SINGLE CORRECT [+4 & -1] 1. Which of the following options is correct regarding the following statements ? Statement - 1: AS; NH,(g)& AS;PCI,(g) <0 ‘Statement - 2 : On heating a metal entropy of metal increases. Statement -3: AS;N..,, = 0. (A) All the statement are correct (B) Only statement - 3 is incorrect (C) Only statement - 1 is correct (D) All statememnt are incorrect Ans. (B) Sol. Statement - 1 N,(g)+3H,(g)—— 2NH,(g) P,,+2Cl, —9PCl,,, as Ang <0 AS,NH,,¢<0 AS,PCI,,g>0 Statoment-2 On heating entropy of metal increases nC,dT qh f Statoment-3 Nyy NA) —ASNag, <0 Ang <0 2. Which of the following options represents correct sequence of True(T} or False(F) statements. Statement - I No Gibbs free energy change occurs four vapourisation at tiple point. ‘Statement - II Entropy driven processes are spontaneous at high temperature. Statement - III AG® of a reaction will increase with increase in temperature if the reaction is endothermic. (AyTTT (B)TTF (C)FTF (D)TFF (B) ST- 1: At triple point all three states are in eq” with each other, hence AG, , ST-2:AG-TAS at T increases, AG becomes more and more negative ST-3: AG? =-RT ink For endothermic reaction as T increases K increases <. AG? willdecrease as T increases, CHEMISTRY, 7 [JLN-Central SRG]Potential Energy/mol—» 3. Reaction coordinate Butane exist in various coformations in nature like in staggard and in ectipsed form. Atany given instant, the probability that a given butane molecule isin anti, gauche, eclipsed-(E,) and in eclipsed-2(E,) conformation is 0.7, 0.2, 0.06 and 0.04 respectively If the molar enthalpy of combustion of natural butane is -690 k Calimol at 25°C. Calculate magnitude of Enthalpy of combustion (kcal/mol) of butane if all the butane molecule are in anti conformation. (a) 691 (B) 690 (c)689 (0)692.7 Ans. (C) 4. Which of the following optitons contains correct set of cases where entropy of system is increasing ? Case-I Dissocication of ammonia gas into N, and H, gases. Case-Il Polymerization process of ethene to form polythene. Case -IIl Adiabatic reversible compression of an ideal gas. Case -1V Condensation of HO) 9) t© give Hj Case-V Isothermal free expansion of ideal ges. (A) Allthe cases (B) Case -I, Ill and V only (C) Case =I, Iland V only (D) Case ~ I Il ll and V only ‘Ans. (B) Sol. (A) 2NH,(g)—>N,(g)+3H,(g) (B) _Duringpoiymerisaion AS J, due to chain formation. Vv, BREN foritreversible compression (T, ),, > (T;), ( AS=nC,,,.4 = AS>0 \. 0) AS=ARM > for fre expansion (V, > V) 5. _Ifisobserved that on combustion of 5.6 gm of but-Lene(q) 70 Kcal of heat is liberated in a closed rigid vessel at 300 K. What could be a possible value of AH®, of but-2-one at same temperature. (A)-701.8Keal/mole —(B) -705 Kcal/mole (C}~700 Kealmole (D)-710 Kealimole Ans. (C) Sol. C,Hs(a} +60p(g) —>4C0 (a) + 4H,0(/) 56am Inclosed rigid vessel V = constant aye — Kea 56 — 700 Keal 56 SH®= AU? +An,RT CHEMISTRY, 2 [JLN-Central SRG]32x 300 1000 =-701.8 Keal/mole AH is calculated for but-1-ene in the problem AH®, of but-2-ene is required which is less than in magnitude compared to AH”, =~700Kcal ~ Keal ONE OR MORE THAN ONE CORRECT [+6 AND -2] 6. Asubstance ‘A’ has the following variation of vapour pressure with temperature for its solid state and liquid state. Identify the options which are correct: 2000 iy 1500 T Data : For solid A: logy. P = 4~ For liquid A : Jog,, P =3.48— Where Pisin mm of Hg and Tin K. (A) Enthalpy of vapourisation and enthalpy of fusion willbe temperature independent, (B) AH.,, willbeapproximately 9.212 kealimol (C} AH). willbe approximately 2.303 kcal/mol (D) AH, willbe approximately 6.909 kealmol ‘Ans. (ABCD) COMPREHENSION TYPE [+3 AND -1] Paragraph for Q.7 to Q.9 Onorder to analyse phase equilibria involving only solids, thermedynamie data are required for calculation of ‘equilibrium constant. From the given data, answer the questions that follow. AHP 4, Of graphite = ~394 kJimole S), graphite = 5.84/K miole AP eq Of diamond = ~396 ki/mole S,, diamond Density of graphite = 2.3 g/ml Density of diamond = 3.5 gm/ml both densities can be assumed to be independent of temperature and pressure. Using the data given and assuming that heat capacities of the two allotropic forms are approximately same, answer the questions that follow. 2.4.d/K miole 7. The value of AGgp for the reaction C, (al2kd (B) 10413 ( (D) equal to: 1022 kd (D)3.02 Ks C gape) = Coviamona AH, = AHCigaptite) ~ AM GyDiemana) = “394 - (-396) +2.0kd/mol AS! = AS, ~ AS craphte) = 2.4 -5.8 = -3.44/K—mole Seman AG? = AH®-TAS® 2.0 -300 x (-3.4 x 10°) 0 + 1.02 = 3.02 8. The pressure at which graphite and diamond willbe at equilibrium ata temperature of 300 K. {A} 1 bar pressure (B) 10" Pa (C) 10° Pa (D) 1.7 x 10°Pa (D) dG = VaP - Sat = vaP J 4c) -avfar = AGP -AG°= AVIP-1) CHEMISTRY, 3 [JLN-Central SRG]{since 1 atm = 10° Pa) 11 6 3020 x 2.3x3.5x10° 3020 = 12] — -— |x10x(P-10°} =10 +e E 3 ) P2102 = 1.6881 x 10° Pa. = 1.7 x 10°Pa 9. _Atwhat temperature can the equilibrium be attained between graphite and diamond at I bar pressure. (A) 500K (B) 200K (C)2000K (D)Atno temperature Ans. (D) Sol. Equilibrium pressure is 1.7 x 10” Pa, Hence, at 1 bar, equilibrium cannot be attained at any temperature. Paragraph for Q.10 to Q.12 Enthalpy change for a chemical reaction can be calculated from bond enthalpy data. Bond enthalpy depends upon structural environment of the bond. For exampke in PCI, bond enthalpy of axial PCI bond is different from bond enthalpy of equatorial P-Cl bond. From the data given below, answer the questions that follow [Given data : AH,PCls(g) = -320KJ/ mole, AH,P(g)= 315KJ/mole , AH; PCI5(g) = 400K mole 10. Calculate the bond enthalpy of P-Clin PCI, if enthalpy of atomization of Cl, (g) = 240 KJ mol. (A) 331.67 KJ mot" (B) 220 Kd mot? (C) 160 KJ mot? (D) 320 Kd mot* ‘Ans. (A) Sol. PCL, -> Pia) + 3Clla) 3xP-Cl = 315 + 3 x 120- (-320) = 315 + 360 + 320 pc = °° = 381.67Ksmot* 11. _ From the data given below (in question and comprehension), calculate bond enthalpy of P-Cl axial bond in PCI, (A) 40 KJ mot (B) 80 Kd mot* (C) 160 Kd mor (D)320 KJ mor Ans. (C) Sol. PCI, PCL + Cl, 2 X'(P ~ Cl) qq) (C1—Cl} = ~320 - (-400) OR, 2 (B=Cl),.y = 240-320 + 400 = 320 (PCy = 22 =160KI mot * 2 12. Calculate enthalpy of formation of C (diamond) if enthalpy of atomization of C (graphite) = 710 KJ mot” and energy required to break C-C bond in diamond (sofid) = 354.05 KJ mot (A) 2.9 KJ mot* {B) 1.9 Kd mot {C) 3.3 KJ mol {D) 0.9 KJ mot? Ans. (B) Sl. Coc sie) > Crane all 70-25 354.05, 10 — 708.1 = 1.9 KJmol* CHEMISTRY, 4 [JLN-Central SRG]MATRIX MATCH [+8 & 0] 13. Match Column - I containing information about thermodynamic parameters & Column -Il containing chemical reaction occuring at standard conditions. Column - Column - It (A) Atleast one of AH? or AS® should {P) Areaction which is always non-spontaneous at any. benegative temperature (B) [aH] < [aur (Q) Combustion of C,He(a) at 400K (C)_ Magnitude of heatenergy exchanged —(R)__Allotropic transition of white phosphorus to red will be greater than magnitude of phosphorus. non-PV work. (Assuming both have same sign) (8) Melting ofice Ans. (A) - (PQR), (B) - (QS), (C) - (RS) INTEGER TYPE [+6 AND -2] 14, A substance has normal boiling point of 400 K. If AS,,, at 1 atm and 400 K is 100 J/K mole, then calculate | AS | veountng at 1 atm and 200 K for the vaporization process. Cp of substance in quid phase = 50 dimole K C, of substance in vapour phase = 40 d/mole K [Express answer in J/K mole] [Give your answer as sum of digits and fill OMR s! Ans. (3) 400 Sol, AS, = JE — = 100=> AH, 4001005 AH, secandine(28) =~ —999 AS, For reaction M(() —>M(g) Taking T, = 200 K:T, = 400K AH) ~ AH.y, = A(nC,,,)(T =T)) 400 x 100~ AH, = (40—50)(400- 200) AH, 40000 +2000 = 42000 AH, __ 42000 narsntine = D9 200 as, = 210) /molK AS, 1 15, H,(g)+50,(g) —H,0(8) AH = -50Keal at 25°C Calculating magnitude of AH (in Keal) at 65°C. Assume gases behave like an ideal gas. [Given: R= 2 cal’moVK] [Multiply your answer by 100 & sum of digits and fill OMR s1 Ans. (6) CHEMISTRY, 5 [JLN-Central SRG]7 =tR Sol. Coy, = Cro, 3 16. Sol. 17. Ans. Cc aR. PH,0%8) = AC, ~an-(Zr+7m)-| 6-0-2 204 Acc = Asoc + AC, (65-25) (2.5) or AH ue =-50+ 740 = -50-0.1 => 50.1 Keal Coleulate solubility of AgBr in water if AG} of Ag’ (aq), Br (aq) and AgBr (3) are 80, -104 and -100 kd/mol" respectively. 7600 Alldata are given at temperature (1) = ga7a—-p aga gg ® [Given: R = 8.314J/K ~ mole} [Instruction : If solubility is 1.0 x 10 moleflitre then your answer should be .] a AgBr—>Ag* + Br Ke Solubility Ans =7 In how many of the following reaction |AH?| > |AE®], assuming reaction to be occuring at a constant temperatureand pressure. 1) Hp +40, H,010 {il) Combustion of C,Hala) at 400K {Ill DimerisationofNO,(g) _{IV) Fusion of water at 0°C (V} Vaporisation of any liquid atits boiling point. (V1) Dissociation of CaCO, (s} (Vit) Combustion of C,H, at 300 K 6) CHEMISTRY, 6 [JLN-Central SRG]18. Forthe reactions 2H,(g) + O,(g) > 2H,O(¢). The standard entropies of H,(g), O,(a) and H,O(¢) at 27°C are 30 CalK* mol", 50 CalK"! mol and 15 CalK mol respectively Assuming H, and O, to behave as ideal gas (without vibrational degree of freedom) and Cr, ,0%) SCalK" mot Determine magnitude of standard entropy (in alk!) change for the reaction at 177°C. Given :R = 2.Calk" mot, in 1.5 = 0.8 [Divide your answer by 19 and fill OMR sheet] Ans. (4) Sol. AS,,,,=2 x 15 (2 x 30 + 50) = 30-110 = -80Calk* Calk"! mol" Cp, =31-(2 x 7 + 7} = 10CalK* mot! Sou = 80410 1n50 om 300 acme 19. Fora reaction 2A,,, +3B,,, —>2C,,, +D, the given data, AG}A =(200+10°T?)J AG;B = (100+2x10°T*)J AG}C = (20042«10°T?)3 AG;D = (100+10% xT?) Express your answer in kJ and round off to nearest integer. @) 2A(g) + 3B(g)—> 2C(g) + D(g) 9.) calculate the magnitude of AH... of the reaction from Nyscton = [2% [200+ 2% 10°T?] + [100+ 10° TJ] [2 [200 +107 T7]+3[100+ 2x10 °T] AG°= (-200+0.15T*)J = +2003 AG°= VdP-$°dT __atconstant pressure aP=0 AG?=-S°dT d(AG*) = —d(S°)dT -d(AG*) aT agr= -24(AG*) dT AS°=-20.01STI/K AS*=-12J/K AG°= AH®-TAS® AHP= AG? +TAS® = 2200 + 400 x (-12) AH?=~26003 AH?=~2.6kI ds°= CHEMISTRY, 7 [JLN-Central SRG]20. Calculate AH... of KF in acatic acid from the following data. (i) AH... [IKECH.COOH(s)]in acetic acid =-3 kd/mole (ii) AH... [KF (s}] in water = -966ld/mole (ii) AH, [RECH,COOH(s)] in water = ~466 knoe (iv) AH {R (@)] = ~700 kdjimole (v) AF [F(g)] = -1000 keimole (vi) AH, [F--CH,COOH(g)] = -500 ki/mole (vii) AHL, of H-bond betwen F-& CH,COOH = 46 lalfmole (vii) AHL” of CH,COOH(s) = 21 kd/imole [Divide your answer by 4 and fill OMR sheet] Ans. (7) 21. Agaseous reaction A(g)—— Big) isat equilibrium under standard condition and 200 K. Calculate the equilib- rium constant of the reaction at 400 K if AS®,.,..,, = 6 X 10° T? Cal/K: where T is temperature in Kelvin. [Given R = 2 Calimol Kand In 2 = 0.7} Ans. (4) 22, Calculate the magnitude of ring strain energy (Extra eneray due to ringstructure) in (kd/mol) of eyelopropane from the following data : AHIC;H,(a!] = 55: AHICIa) 0: 15.0: 4H [H(a)] BE (C—C) = 355; BE (CH) = 410 (allin ki/mol) [Give your answer as sum of digits and Fill OMR sheet] Ans. (7) Sol. 3C\s)+3H-(g)—> Ala); A\Hlobs) = 55, AH (The retied) = [3 x 715) + (3 x 2 x 220)]— [(355 x 3) + (6 x 410] [2145 + 1320] [1065 + 2460] 3465 - 60 kdjinole. Ring strain energy = AH (Theoretical) — A}H (observed) = 60-55 = -115 kd/moke |Ringstrain energy| = 115 klimole CHEMISTRY, 8 [JLN-Central SRG]