Thermodynamics & Trend Analysis with Importa Topic Name Sub-Topic _[@ns.[Lop|ans.[Lop| ans. [Lop] ans.[Lop]ans.|Lop First law and basic first law of : fundamentals of — |_thermodynamics thermodynamics laws of bond dissociation energy thermochemistry second law of Entropy and second | po nna memics law of thermodynamics entropy w isothermal and adiabatic conditions are as shown in the figure. NET Odisha 2019] Spontaneity and Gibb's |_| spentaniety tala fe Wesenersh t EEasy D-biffieut Topic 1: First Law and Basic Fundamentals of Thermodynamics aman ‘The correct option for free expansion of an ideal gas under adiabatic condition is (2020) t —5E,%7) (a) q=0,AT0 Note) (b) q<0,AT=Oandw=0 (© q>0,AT>Oandw>0 vo @ q=0,AT=0and AB -> Isothermal expansion ‘An ideal gas expands isothermally from 10-3 m? AC — Adiabatic expansion to 10-2 m? at 300 K against a constant pressure Which ofthe following options is not correct? of 10° Nnv2, The work done on the gas is @ TOT, ©) AS oc” Sys INET Odiska 2019] © TT, © Wypee> Wome (@) -900%3 ©) 270K Under isothermal condition, a gas at 300 K (©) -9005 (@ +900K expands Font 01 1.00195 | against a constant Reversible expansion of an ideal gas under external pressure of 2 bar. The work done by the gasis (Given that | Lbar=100J] (2019) @ 30) () Sk © 251 (@) 305Thermodynamics 5. A gas is allowed to expand in a well insulated container against a constant external pressure of 2.5 atm from an initial volume of 2.50 Ltoa final volume of 4.50 L. The change in internal energy AU of the gas in joules will be:- {2027} (@) 5003 (b) ~5055 (©) +505) (@)_ 1136255 ‘The heat of combustion of carbon to CO, is 393.5 kJ/mol. The heat released upon formation 0f 35.2 g of CO, from carbon and oxygen gas is [2015 RS} (@) 315K (b) 815K (©) -630k) @ 315K ‘When 5 litres of a gas mixture of methane and propane is perfectly combusted at 0°C and 1 atmosphere, 16 litre of oxygen at the same temperature and pressure is consumed, The amountof heat released from this combustion in KY (AH gis (CH)= 890 KI mol), MHey (CH) 220k} mob!) is INEET Kar. 2013] @) 2 (b) 38 (©) 317 (d@) 477 ‘Which of the following is correct option for free expansion of an ideal gas under adiabatic condition ? (20u) (a) q-0,AT=0, () 9 20,AT=0, Three moles of an ideal gas expanded spontaneously into vacuum. The work done will be: P2010) (a) Zero (b) Infinite (©) 3 Joules (@) 9Joules Which of the following are not state functions ? © gtw a) q P2008] aw (IY) H-TS (@) andy) (b) (and avy (© (Manda — @_ Aand an Ina closed insulated container, a liquid is stirred ‘paddle to inerease the temperature, which of the following is true? 2002) (a) AE=W20,q=0 (b) AE=W=q20 (© AE 20 (d) W=0,AE=q20 When | mol of a gas is heated at constant volume, temperature is raised from 298 to 308 K. Ifheat supplied to the gas is 500 J, then which statement is correct ? P00i] 1B. Ty 1. Adiabatic expansions of an ideal gas is accompanied by [1999 (a) decrease in AE (b) increase in temperature (©) decrease in AS (@) nochange in any one of the above properties Topic 2: Laws of Thermochemistry ‘The bond dissociation energies of X,, Y, and X¥are in theratioof | :0.5: |. AM forthe formation of XY is -200 kJ mol", The bond dissociation energy of X, will be [2018] (@) 200kImot! —(b)_ 100k mol! (©) 400kImot? —(@)_ 800 kJ mot" ‘Three thermochemical equations are given below: (i) C(graphite) + O4g) > CO,(g); AFP = xk mol"! O,{g) + COW); AgP=ykJ mol 1 Gi) Clgraphite) + 1 Gi) COl®)+ 5 OLg) > COW); AW ~zid mot! ‘Based on the above-equations, find out which ofthe relationship given below is correct? INEET Kar. 2013] Standard enthalpy of vapourisation Aj. ° for water at 100°C is 40.66 kI mol-!. The internal energy of vaporisation of water at 100°C (inkI mol") is Pon} (@) +3736 (b) 43.76 ©) 43.76 @) $40.66 (Assume water vapour to behave likean ideal gas). Equal volumes of twomonoatomic gases, A and B, at same temperature and pressure are mixed. ‘The ratio of specific heats (C,/C,) of the mixture will be: (2012 Mj (@) 088 (b) 150 © 33 (@) 167 Enthalpy change forthe reaction, 2011] AH(g) —> 2H (g) is 869.6 KI. ‘The dissociation energy of HH bond is : (a) —434.8KI (b) ~ 869.6 (© +4348K) @) #21748)19, a. Consider the following processes ‘AH (ki/mol) 12A>B +150 3B92C+D 125 E+A>2D +350 For B+D>E+2C,AHwillbe: — (20/1MJ (a) 525k¥/mol (b) =175k¥/mol (©) -325kiimol ——(@)_-325k4/mol ‘The following two reactions are known : (2010) Fe,03(s) + 3CO (g) —> 2Fe(s)+3CO,(g): AH=-268kI FeO (9)+ CO(g) —> Fe(s) + CO,(g): AH=-165k) The value ot A H tor the following reaction Fe,0,(s) + CO(g) —> 2FeO(s) + CO,g) is; (a) +6.2KI () +103K) (©) -433K) (@ -103KI From the following bond energies: HH bond energy: 431.37 kJ mol! C=C bond energy: 606.10 kI mol! C—Chond energy: 336.49 kI mol! —H bond energy: 410.50 kJ mol! 2009 Enthalpy for the reaction, HOH HOW HH (@) =243.6kI mot (b) -120.0K mot! (©) 553.0kImol —(@)_1523.6kI mot! Bond dissociation enthalpy of H, Cl, and HCL are 434, 242 and 431 kI mol-! respectively. Enthalpy of formation of HCI is 2008) (@ 93kI mot! (b) 245 kJ mor! (©) -93kImol? ——@) 245 kJ mot! Consider the following reactions: (2007) ()-H(aq)+ OH (aq)=H,0(), AH=—X,kI mol (2) = H,00), Ak mol! L(g)=CO(2) | 1LO, (kJ mol-! 1 @ H@* AH Gi) COs) AH 5 (iv) CoHa(g) +5 O2() =2C0,(g) + H,0(0)" AH= +4X,k) mol! a CHEMISTRY Enthalpy of formation of H,O (1) is (@) +XjkImol! (by —XykI mol! (©) +X,kImol- —— @) —X4kI mol! Given that bond energies of H ~ H and C1—Cl are 430 kJ mol-1 and 240 kJ mol respectively and AH, for HCI is—90 kJ mol-, bond enthalpy of HCl is 2007] (a) 380KS mol! (b)425kF mol! (©) 245kJmol! ——(@)_290kI mol! ‘The enthalpy of hydrogenation of eyelohexene is—119.5 kJ mol-" Ifresonance energy ofbenzene 150.4 kJ mol-!, its enthalpy of hydrogenation ‘would be 12006] (@) 208.1 KIuwl)— (&) ~209.9 I ul # (©) -3585kImol —(@) ~508.9kI mol! Assume each reaction is carried out in an open container. For which reaction will AH= AE? 12006} (a) C(s)+2H,0(g) > 2H, (g) + CO,(2) (b) PCIs(g) PCI, (2) + Cl (@) (©) 2CO(g) +0, (g)>2C0,(2) (a) Hy (g) + Br,(g) > 2 HBr (g) The absolute enthalpy of neutralisation of the reaction: MgO (s)+2HCI (aq) —> MgCl, (ag) +H,0 0) will be 2005] (@ -$7.33kImot (b) Greater than —$7.33 kJ mol“! (©) Lessthan -$7.33 kI mol"! (@)_ $7.33kI mor" If the bond energies of H—H, Br—Br,and H-Br are 433, 192 and 364 kl mol! respectively, the AFP for the reaction P2004] H(g)+Brp(g) > 2HBr(g) is @ -261K) (&) + 103k (©) +261K (a) — 103K The work done during the expansion of a gas fiom a volume of 4 dm? to 6 dm? against a constant external pressure of 3 atm is (1Latm = 101.32) 2004 (a) -63 (b) —608) fo) +304) (@ -304) ‘The molar heat capacity of water at constant pressure is 75 JK-! mol!, When 1kJ of heat is supplied to 100 g of water, which is free to expand, the inerease in temperature of water is (a) 66K (b) 12K (2003) (©) 24K (@) 48KThermodynamics 2 33 38 39, ‘The densities of graphite and diamond at 298 K are 2.25 and 3.31 g cm, respectively. If the standard free energy difference (AG°) is equal to 1895.J mol, the pressure at which graphite will be transformed into diamond at 298 K is (2003) (a) 9,92 10Pa (b) 9.92 108Pa (©) 9.92=107Pa—(@) 9.92 106Pa For which one of the following equations is APP pac, ual to AH? for the product? [2003] (a) 2CO(g)+02(g)—> 2CO9(g) (b) N2(g) +03(g) > N203(g) (©) CH4(g)+2C1(g) > CH Clay) + 2HCI(g) (d) Xe(g)+2F,(g) > XeF,(g) For the reaction CyHg(g)+503(g) > 3CO3(g)+4H00) at constant temperature, AH ABs (2003] (a) -RT () +R7 (©) -3RT (@) +3R7 Heat of combustion AFP for C (s), Hy (g) and CH, (g) are -94, -68 and -213 kcal/mol, then AIP for C(s)+2Hp(2) > CH 4(e) is (2002) (a) -17kcat (by SH kcal (© -170keal (d),-85 kcal Enthalpy of CHy +40, >CH;OH is negative. Ifenthalpy of combustion of CH, and CHOH are x and y respectively, then which relation is correct 001 (@) xy (b) xsy © x= @ x2y ‘What is the enthalpy change for, 2H02(1) > 2H,0()+0(g) if heat of formation of H,O, (I) and H,O (1) are —188 and ~286 k/mol respectively? 001 (a) -196ky/mol (b) +948k/imot (© +196klimol ——(@)_-948K/mol The values of heat of formation of SO, and SO, are-298.2 kJ and-98,2 kJ. The heatof formation of the reaction 2000) $02 +(1/2)02 > S05 will be (@) 200K) (b) 356.23 (© +200K (@) ~396.2kI For a cyclic process, which of the following is not true? 1999} (a) AH (b) AE: (A (d) Total W=0 For a reaction in which all reactants and proxiucts are liquids, which one ofthe following equations is most applicable ? 1999) 4 2. 4. 46. (a) AH 2003 :AH"=—y KI the enthalpy of formation of earbon monoxide will be 11997] avy =28 @ ry (Olery (©) 2-y (@ y-2 Hydrogen has an ionisation energy of 1311 kJ mol-! and for chlorine it is 1256 kJ mol, ‘Hydrogen forms H’ (aq) ions but chlorine does not form Cl’ (aq) ions because 11996] (a) H has lower hydration enthalpy (b) Clas lower hydration enthalpy (©) Clhas high electron affinity (@)) Clhhas high electronegativity If enthalpies of formation of CyHa(g) + CO) and H,0(1) at 25°C and atm pressure are 52, ~ 394 and — 286 kJ/mol respectively, the enthalpy of combustion of C3H, is equal to 11995] (a) -1412kmol —(b) ~ 1412 Kd-mol (©) +142Kiimol — (@) + 1412 KU'mol Equal volumes of molar hydrochloric acid and sulphuric acid are neutralized by dil. NaOH solution and x keal and ykeal of heat are liberated respectively. Which of the following is true ? 11994) 1 (a) x=y (b) x=5y (© x=2y @ Noné of these For the reaction 11994) No +3H) =——=2NH, SH=? (a) AE+2RT () AE2RT (©) AH=RT (@) AE-RT. ‘During isothermal expansion of an ideal gas, its 11991, 94] (@) internal energy increases (b) enthalpy decreases (©) enthalpy remains unaffected (@)_ enthalpy reduces to zero,41. 49. 50. SI 2. 3 If AH isthe change in enthalpy and AE, the change in internal energy accompanying a gaseous reaction, then 11990) (@) AM isalways greater than AB, (b) AH and AS<0 (b) AH0 (©) AHsOand AS<0 (@) AH>Oand AS>0 In which case change in entropy is negative ? 2019) (a) Evaporation of water Expansion ofa gas at constant temperature (©) Sublimation of solid t6 gas. (@ 2H(@)> He) ‘The enthalpy of fision of water is 1.435 keal/mol. ‘The molar entropy change for the melting of ice ato" [2012] (@)10.52cal/(molK) (b) 21.04eal/(molK) (©) 5.260cal/(molK) (d) 0.526cal/(molK) Ifthe enthalpy change for the transition of liquid ‘water to steam is 30 kJ mol! at 27°C, theentropy change for the process would be: [2011] (@) 10Jmol1K7 —(b) 1.0) mok"K7 (©) O.1JmoltK7 — (@) 100Jmol1K#* Standard entropies of X, Ypand XY, are 60,40 and 50 JK-'mol-" respectively. For the reaction, 13 SXptty XH, AV =—30KI 202"9 2 5 tobe at equilibrium, the temperature should be: 2010) (@) 750K (&) 100K (© 250K (@ 500K For the gas phase reaction, 2008] PCl(g) ——= PCI(g) + Cl(e) which of the following conditions are correct ? (a) AH=Oand AS<0 (b) AH>OandAS>0 (c) AHOandAS<0 7. 61. CHEMISTRY What i the entropy change (in JK-! mol-!) when ‘one mole of ice is converted into water at 0°C? (The enthalpy change for the conversion ofice to liquid water is6.0kJ mol-!at °C) /2003] (a) 21.98 (b) 20.13 © 20183 (a) 2198 2 mole of an ideal gas at 27°C temperature is expanded reversibly from 2 it to20 lit. Find the entropy change(R=2cal/molK) (2002) @ 21 ) 0 wo 4 @ 92 Unit of entropy is 002 (@) JK"! mol! (b) Jmol (©) F'K'mol? —— @)_JKmot ‘The entropy change in the fusion of one mole ofa solid melting at 27°C (Latent heat of fusion, 2930 J mob!) is: 2000] (a) 9.773K-1mol-! (by 10.73) Kl mol"! (©) 2930JK-! mol! (@) 108.5) K-! mol-! Identify the correct statement regarding entropy: 11998} (a) At absolute zero of temperature, entropy ofa perfectly crystalline substance is taken to be zero At absolute Zero of temperature, the ‘entropy ofa perfectly crystalline substance istve (©) At absolute zero of temperature, the entropy of all crystalline substances is taken to be zero (@ At O°C, the entropy of a perfectly crystalline substance is taken to be zero According to the third law of thermodynamics which one of the following quantities for a perfectly crystalline solid is zero at absolute (b) ze10? 11996} (a) Frecenergy —_(b)_ Entropy (©) Enthalpy (4) Internal energy Given the followingentropy values (in JK mol!) «1298 K and 1 atm :H(g) : 130.6, Cl, (8): 223.0, HCI (g) : 186.7. The entropy change (in J K-! mol!) for the reaction Hp(g)+Cl(2)—>2HCl(g) is 1996) (a) +5403 (b) +7270 (©) -1669 (@) +198 A chemical reaction will be spontaneous ifit is ‘accompanied by a decrease of 11994] (a) entropy of the system (b)_ enthalpy of the system (©) internal energy of the system (d)_ free energy of the systemThermodynamics a. 6 ‘Topic 4: Spontaneity and Gibb's Free Energy For a given reaction, AH = 35.5 KI mol and AS=83.6.)K"' mol". The reaction isspontaneous at (Assume that AH and AS do not vary with temperature) (2017) (@) T>425K (b) All temperatures (©) T>298K (@ 7<425K The correct thermodynamic conditions for the spontaneous reaction at all tempertures is 2016) (a) AH>OandAS>0 (b) AH >OandAs<0 (©) AHO (d) AHCO®) ©) COW)+ F040) COL) 1 Mg(s) + 5 Ox(e) > MgO(s) 1 1 1 (FC (eraphite) + 50,)> 5 Coxe) For vaporization of water at | atmospheric pressure, the values of AH and AS are 40.63 kcimot-tand 108.8 JK“! mol-, respectively. The temperature when Gibbs energy change (AG) for this transformation willbe zero, is: 12010) @) 294K () 234K (©) 334K (@ 374K Match List-I (Equations) with List-I (Type of processes) and sclect the correct option. /2070) List I List I ‘Type of processes @) k,>0 (Non-spontaneous @) kG 2CO(w) are 170 kl and 170 JK-", respectively. This reaction will be spontaneous at 12009] @ 910K () 10K, (©) 510K (@ 710K The enthalpy and entropy change for the reaetion Br,{l)* Cl, (@) >2BrC1(g) are 30k] mot-l and 105 JK! mol! respectively. The temperature at which the reaction will be in cequilibriumis 12006] @ 23K (b) 450K (© 30K (@) 285.7 Identify the correct statement for change of Gibbs energy for a system (AGjymq) at constant temperature and pressure 12006) G@)- 1PAG,.,.,, = Oethe system has attained equilibrium (b) FAG, | the system is still moving in particular direction HAG 40, the process isnot spontaneous (@) AGgree> 0, the process is spontaneous A reaction occurs spontaneously it (20087 (@) TAS AM/andboth AH and AS are + ve (b) TAS> AMand AM is+ veund ASis —ve (©) TAS> Al/andboth AH and AS are + ve (@)_TAS= AH andboth AH and AS are+ ve Which of the following pairs of a chemical reaction is certain to resi in a spontaneous reaction? 72005) (a) Exothermic and increasing disorder (by Exothermie and decreasing disorder (©) Endothermic and increasing disorder (@) Endothermicand decreasing disorder Standard enthalpy and standard entropy changes forthe oxidation ofamimonia at 298K are ~ 382.64 KJ mol" and -145,6 JK-! mol-!, spectively. Standard Gibb'sencegy change for the same reaction at 298 K is 2004) @ 221kimol" (by -3393k mot! (©) -A39.3k mot! (d) $232k mol ©74, Considering entropy (5) as a thermodynamic parameter, the criterion for the spontaneity of any process is 2004) (2) ASygiem + ASyuroundings > (©) ASgstem~ASuroundings (©) ASSem > 0 only (@) AS.urroundings * 9 only 76. 75. The factor of AG values is important in metallurgy. The AG values for the following reactions at 800°C are given as S3(s) + 20(g) —> 280() 3 AG 2Zn(s)+S_(8) —>2ZnS(s) : AG CHEMISTRY 2Zn(s) + O2(g)—> 2ZnO(s) : AG= 480k ‘Then AG for the reaction 2ZnS(s) + 302(g)—> 2Zn0(s) + 2802(s) will be 2000] @ 3571 (b) 731k © BW (@) 22010 Consider the following reaction occurring in an automobile 11994) 2CsHis(g) + 2502(g) 9 16COp +18H20(8) the sign of AH, ASand AG would be ) ANSWER KEY 33] (c) [4 (by 34 | (a) [2 (by 35 36 B 4 @) @ b) (by a7) b) 5, >4-0 AE =nC,dT > AE =0 So, q=0,AT=0,w=0. 10\(102— 107) =-900 (a) Since graph A to C represents adiabatic reversible expansion, so work is done on the expense of intemal energy, therefore, there is decrease in internal energy. So the temperature decreases 6 1 =-2(0.15)=-03 L Bar =-0.3 « 100J=—30I (b) The system is in isolated state For an adiabatic process, q= 0 2Satm x (45-2.5)L $x 2Latm Sx 1013) 06,5 5-505) (@) C#+0,> CO, +393.5kdimol 2g Mg 44g.CO, is formed from 12g ofcarbon 12352 35.2gis formed from of C =9.6g of C=9.6/12=0.8 mole 1 mole release heat 393.5 KI O&moale release heat= 304 $ 08 =3148kJ ~315K) (©) CH, +20) —>CO,+2#,0 C3Hg + 30) —>3C0, +410 G2 55-9)Thermodynamics IL. 2, 2B 2x+5(S-a)=16 = r=3b Heat released 3 2 5 8904+ =x 2220 =317 24 24 (6) For adiabatic process AQ=0 In free expansion, external pressure is zero. ‘Thus, work done W=0and AE =W=0. If (@) Ideal gas during spontaneous expansion into vacuum does not do any external work (@) We know that q (heat) and work (i) arenot state functions but (g + w) is a state functions. H-TS (ic. G)isalsoa state function. @) Internal energy is dependent upon temperature and according to first law of thermodynamics total energy of an isolated system remains same, ie., in a system of constant mass, energy ean neither be created nor destroyed by any physical or chemical ‘change but can be transformed from one form to another AE=q+w For clase insulated comaines, ¢ = 0,50, Ade 173s work is dane on the Sysext (b) As volume is constant hence, work done in this process is zero hence, heat supplied is ‘equal to change in internal energy. (a) AE=AQ-W Foradiabatic expansion, AO=0 SAE=-W ‘The negative sign shows decrease in Internal ‘energy, which is equal to the work done by the system on the surroundings. (@) LetB.B of X,, Y,and XY arexkJ mol, 0.5xkJ mol and.xki mol" respectively 200k mol! Leedy, oxy al AH=-200= B.Dpentas2(B-E)pptt Tae! ¥[ac sos ace On solving, x=800 kJ mot (©) Applying Hess's law, equation (i) can be ‘obtained by adding equations (ii) and xaytz () Avgp = 40.66 kJ mol! T= 1004 273-373 K,AE=? AH=AE + An,RT => AE=AH—An,RT ‘An, = number of gaseous moles of products = number of gascous moles of reactants H,01=H,0@) ‘Ang=1-0=1 AEM AH -RT AE= (40.66 * 103)—(@.314 373) =37559 Jimol or 37.56 KI ‘mol 17. @) Foramonoatomic gas G waa pron CE =1.29 deg of ok ~7 G E71 SB itdegre of ieedom = 6 18 (©) Given 4H(g) — 2H (2); AH = -869.6 KI 0 2H2(g)—4H(g);, AH = 869.6 KI (2) —92H(@); aH = "SS pass 19. (b) Given AH Fp +150 a) 3B—32C+D -125 Ab) E+d—32D +390 ) Tocalculate AH operate 2 eq, (a) +04. (b)-e4.(0) ‘AH=300~125~350=—175 20. @) Fe,0,(s)* CO(e) + 2FeOKS}+ CO,(e) Given Fe,O,(s}+ 3CO(g) > 2Fels)+ 3CO4(e) ; AH=—268KI (i) FeO(s) + CO(g) + Fels) + CO,(g); AH=-I65kI—...(ii)CHEMISTRY “AH for the reaction The resonance energy provides extra stability Fe,0,(3) + CO3(2) > 2FeO(s) +CO,Ce) to the benzene molecule so it has to overcome can be caleulate as for hydrogenation to take place. So AH=— 358.5 150.4)=—208.1 kI eqn i) 2 eqn Gi) » AH=268+330=+6.2k) 21. (b) Enthalpy ofreaction ee eee (©) Enthalpy of eactio increases the stability. Hence, tne magnitude of ‘Beacan) ~B-Emodue) enthalpy of hydrogenation wil be less than the = [Bio 4BE m+ BEG] Gre ein 26 (@) Weknow that -[BE cc) + 6BEC-1 | AH=AE+ PAV = [606.1 + 4410.5) +431.37)]-[386.49 In the reaction, H, + Br; —> 2HBr thi *1(6"4103)) change in volumeor A =-12001) molt So, AH= AB for this reaction 22. (©) The reaction for formation of HCI can be written as If the container is closed then pressure is not Hy +Cl, >2HC1 constant and AH = AE +V AP H-H¥CI-Cl>2(H-Cl) Substituting the given values, we get enthalpy 27. () As MgO is a oxide of weak base hence of formation of some energy is lost to break MgO (3). Hence Myc) (BB ®Bacl Fe enthalpy is less than -$7.33 kJ mol", * . 2 =434+242—2 x (431)=—I86kI “ 2% @ me Br(g) 9 2H) . Enthalpy of formation for = (BE )pcactan (BE) product = (4334192)—(2x364) 3k » 23. (@) This reaction shows the formation of HO, and the X; represents the enthalpy of formation =~3(6—4) =—6 litre atmosphere ofH,0. 6x 101.32 =-608) =753K! mol! ‘The enthalpy of formation is the heat evolved or 5 (©) Given C, absorbed when one mole of substance is formed from its constituent atoms 00 ja ™ Q= 10005 ar? = nC AT 24. (6) SH) +4C; —+ HCL one () ZH +zCh ar 1000818 94K AH yc = J) BE. of reactant 31, (N) Change in volume from I mole of graphite to | mole of diamond = BE.of products mole ofdiame 3 1 1 av 1.71 em’ ~90 = 5430+ 5240 BE. of HCI =-171 «106m ©. BE.of HC1=215+120+90 Gibb's free energy is the measure of useful work = 425 KI mol"! done at constant temperature and pressure. AG=-pAV = 6 CnC we ise i 2 Pe AV 1.71x107m> Chun 111? CC). ai-se195 11s 10"Pa 32. (d) Ny(g)+ Ox(g) —> N,O,(g) =~358.5kIThermodynamics 3. 36, 37, The state of N. Thus, this reaction is not equal to AH? for the product (@ Xelg) + 2F,(@) —> XeF (g) For thisreaction AH? is equal to AH? of XeF,(g). (a) C(s)+O2(g) > COz(g) AH = —94 kcal/mole ..(i) Hy(g)+40) + 1,0(8) AH =~68 keal/mole.(ii) CHy +20) + CO, +2H,0, (AH = ~213kcal/mole ...(iii) C(s)+2Hy > CHy(g), AH =? iv) Eqn. (iv) can be obtained by eq. (i)+eq. (il) 2 eq) C(s}+O2(g) > CO>(g) 2H (@)+09(8) > 2H,0(8) CO>(g)+2Hy0(g) > CH (2) + 203(@) C(s) + 2H) (g) > CH4(g) $0, Aen, ==94 + 2-68)— 213) =~94—136+213=-17kcal/mole (a) The enthalpy of combustion is always negative. CH, +20, —+ CO,+ 2H HOH 30, — 900, +2H,0,4H, Hy =k kl i, 10, 900 AH a It is given that AH = is negative. Thus, -x-Cy)=~ve yoxs-ve Hence, “x> y. (@) 24,0, (1) —>2H,0() + 0,(g) AH =? AH =[2* AH, of HyO(1)+(AHy of Op) ~OxAHy of Hz02q))] [(2 «(-286)) + (0) —(2«(-188))] =[-572+376|=—196 kI/mole © 80, +50; —»503 All = AHF (505) S47 (S09) =-98,2+298,2=200kI/Mole 4 RG (@) For acyclic process AE =0, AH =0 & AG =0. Asall depend upon final state and initial state,W doesn’t depend ‘on path followed. (©) As all reactant and product are liquid An(e) AM = AE~ AuRT AH = AE (An =0) (b) Foran isothermal process AE=0 () Given C+03 =CO5, AH®=—=xkI a) 2COz = 2C0+0y AH?=+ykI (0) or CO: =CO+1/203, AH*=+y/2KI (Cc) From eq. no. (a) and (e) 2 (b) Hydration energy of CI* is very less than H?, hence it doesn’t form Cl (aq) ion. (b) Enthalpy of formation of C)H4,CO, and HO are 52, — 394 and ~ 286 kJ/ mol respectively. (Given) ‘The reaction’ CaHy +303 >2CO} +20. change in enthalpy, (AH) = AH products ~ AA reactants x(-394) +2x(-286) —(52+0) 1412 ki mol. (b) 1MH,S0,=2g eq, of HCI Hence y=2xor x () Any 2, AH= AE-2RT. (©). During isothermal expansion of deal gas, AT=0. NowH=E+PV AH =AE+A(PV) AE+ A(aRD); AMT e.,remain unaffected. (@) As AH=AE + An RT ifm, 2Cl(g) is endothermic reaction because it required energy to break bond.49. 3h. 92, 53, 55, So reverse reaction, 2C1(g)—+Cl, (g) Will be exothermic, A,H <0 Also, two gaseous atom combine together to form | gascous molecule, @ In 2H(g) ~~ Hy(g), n0. of motes decreases, therefore entropy decreases. AM 1435x109 Tr 2 = 5.260 cal/ mol —K (@) Givens = 30 ks mo T=273 +27=300K © as asp= Slit 3210" y grt T 300 =100J mol! Kt @) AS for thereaction pdt =i 405 aH-TaS AS =50-(30+ 60) For equilibrium 4G «Hy =30000 ss) -40 (b) Forthereaction PCIs(g) = PCl;(g) +Cl(z) The reaction given is an example of decomposition reaction and we know that decomposition reactions are endothermic in nature, he, H > 0. Further an=(41)-1=41 Hence more number of moleculesare present in produets which shows more randomness i.e. 5 5>0 (+ Sis positive) Tr aH @ as-% _ AM per mole _ 6000 AS{per mole) = PE 7 + 21.98 JK> !mol"! (@ For isothermal reversible expansion nRT 2.303 log 4 CHEMISTRY = 22% 72303 1=92T Entropy change, as == 227. 9.2cal 56 (@) Asa g— required heat per mole T— constant absolute temperature Unit ofenttopy is JK"! mol! Latent heat of fusion _ AM, Melting point T s7, yal"! = 9.77 Kl mol! 58 (a) We know from the third law of thermodynamics, the entropy of a perfectly crystalline substance at absolute zero temperature is taken to be zero, 59 (b) Entropyis zero for perfectly crystaline solid ‘at absolute zero. £ eee ise eee eet Bah ipsaayT peer of in De biked td boo @. (@) Entropy change AS= AS roduc ~ASpeactant =2 (186.7) ~(223+ 130.6) 73.4- 353.6 =19.85K" mot 61. (@)_ + Gisnegative for a spontaneous process. € (a) Givens 1 35.Sk} mol 5 5=83.6JK"! molt vaG=sH-TLS For a reaction to be spontaneous, » G=—ve ie sH< TS AH _ 355x103 Jmol“! > Ait _ 35.5%10° Jmol” as 83.6JK" So, the given reaction will be spontaneous at T245k @. (© «G=sH-TaS Fora spontaneous reaction s G=—ve (always) ‘which is possible only i sH0 spontaneous at all vemperacures, 64 (b) Givens U=2.1 keal,s S=20¢al. K"! 00K Hams UtankT Putting the values fiven in the equationThermodynamics 67. AH= 2.142% x 300 1+1,.2=33 keal. Now, AG=AH-TAS 20 =33-300x 9 2.7 cal 3 a « (@) Since, in the first reaction more (An > 0) gaseous products are forming from solid carbon hence, entropy will increase i.e AS= He. Cer) + $x) > CO(g); AS”=+ ve Since, AG? — AM” — TAS euce the value ¥EAG decrease on increasing temperature. @) HO, H,0(g) AH =40630 Jmol“! AS = 108.8 JK molt AG = AH TAS When AG=0, AH —TAS =0 _ AH _ 406303 mol! SE AS" 108,83 mol (@) When Kp>Q: Rate of forward reaction > Rate of backward reaction 2. Reaction is spontaneous Q) When AG? K AH, AG=AH-TAS ‘When AH>0 and TAS> AH then AG <0. Henee, reaction is endothermic and spontaneous, (b) AG=AH-TAS Atequilibrium, AG=0 2 0=(170 108 J)-7(170JK-!) = T= 100K For spontaneity, AG is — ve, which is possible only if 7 > 1000 K. (@) We know that AG=AH-TAS n RB. ‘When the reaction isin equilibrium, AG=0 o=an-ras > 7-At AS _ 230%1000 ago 2% 105 (@) If AG gem = 0 the system has attained equilibrium: IAG <0, the provess is spontaneous IfAG > 0, theprovess does not occur in the forward direction. Itmay occur in the backward direction. (©) For a spontaneous reaction AG(-ve), which is possible if AS = +ve, AH= +e and TAS> AH [As AG= AH- TAS) (a) Measure of disorder of a system is nothing but Entropy. For a spontaneous reaction, AG <0. Asper Gibbs Helmholtz equation, (b) AG = An -Tas 382.64 —(—208%145.6x103) =-339.3 kJ mol”! (@ For a spontaneous process, AS.) is always positive (©) For the reaction 2 ZnS »2Zn+8, ;AG,°=293 KI 2Zn+0,>2Zn0 AG,"=—480 kd. 8, +20,4280, :6,¢ SG" for the reaction 2Zn$+30,32Zn0+2S0, can be obtaitied by adding equ. (i), (i) and (iit) => AG'= 293-480-544 =—731 KI (©) Thisis combustion reaction, which is always exothermichence AH=—ve ‘As the no. of gaseous molecules are increasing hence entropy increases now AG = AH TAS For a spontancous reaction AG =-ve Which is possible in this case as AW =—ve and AS= he,Equilibrium & Trend Analysis with Important Topics & Sub-Topics Topic Name SubTepic__|ons.[too|ons.[Lop| ons. [Lop]ons.[top |ons.[Lop| Lawof mass action, equilibrium equilibrium ata constantand its} constant/Kp and Ke application relation between K oe ada 1 |o Relation between «,Q | Le-chatelier da andGandfactors | principle __| |_| | | | "| affecting equilibrium | _ Clausius and Clapeyron's rte equation Bronsted acid and ile Theories of acid and bases bases,ionic product of water and pH scale pH scale afe]a jo Commonioneffectsalt| solubility a|o 1A hydrolysis, buffer solution and solubility Ksp afa}a]fafafa product E- Easy D- Difficult Topic 1: Law of Mass Action, Equilibrium ‘The equilibrium constant (K) of the reaction Constant (K, and K,) and its Application > 55. 2 nos : «, y) ppt 2NH; +20, === 2NO + 3H,0, will be; 1. Theequilibrium constant ofthe following are a ce Ny +3H, =2NH, Ky por (@) K)K3/K) © KKK, Ny+0)42NO Ky (©) 3K IK, @ KKK H, +40, >H,0 n> eEquilibrium 2 A.20 litre container at 400 K contains CO,(g) at pressure 0.4 atm and an excess of SrO (neglect the volume of solid SrO). The volume of the container is now decreased by moving the movable piston fitted in the container. The ‘maximum volume of the container, when pressure of CO, attains its maximum value, will be (Given that: StCO, (s) = S10 (5) +CO,(e). Kp =L6atm) O17] (a) 10live (b) litre (© 2litre (@) Stitre If the value of an equilibrium constant for a particular reaction is 1.6 x 10!2, then at ccquilibrium thesyotem will eontain: | 2025 (a) mostly reactants (b)_ mostly products (©) similar amounts of reactants and products (d)_allreactants Ifthe equilibrium constant for Na(g) + O4(g) == 2NO(E) is K, the equilibrium constant for 12015 RS} l 1 , 5 Nalo)+ 503(2) = NO) will be: 3 1 @ © 3K @K @R Given that the equilibrium constant for the reaction 280,(g) + Oy(g) = 2804¢¢) has a value of278 ata particular temperature. What is the value of the equilibrium constant for the following reaction atthe same temperature ? 1 $03(8)-S02(8)+502(8) (2012 M] (@) 18105 (b) 3.6% 10% (©) 60% 107 @_13%105 Given the reaction between 2 gases represented by A, and B, to give the compound AB(g), Ax(e) + Bg) == 2AB(9), At equilibrium, the concentration 0* 109M 42% 103M 8x 103M If the reaction takes place in a sealed vessel at 527°C, then the value of K, will be: (2012 Mj @ 20 ) 19 (©) 08 @ 45 For the reaction No(g) + 03(g) == 2NO(g), the equilibrium constant is K,. The equi ‘constant is K; for the reaction 2NO(g) + O,{g) —= 2NO,(g). What is K for the reaction NOs(g) —= $N@) +00? Pony @ 1/QK,Ky) () 1/4K,K,) (© [If KK)” @) 1/(KK) In which of the following equilibrium K, and K, arenot equal? 2010} (@ 2NO@®) = N2(g)+Or(8) (b) SO3(g)+NO>(g) = SO3(g) + NO(g) ©) Hy(e)+h(@) = 2Hlle) @ 2C(s) +0, = 2COAg) ‘The reaction 24(g) + B(g) = 3C(g) + Dg) is ‘begun with the concentrations of 4 and B both atan initial value of 1.00M, When equilibrium is. reached, the concentration of D ismeasured and ‘ound tobe 0.25 M. The value forthe equilibrium constant for this reaction is given by the ‘expression Pom (@) (0.75) .25)] + (0.757 (025)] (©) [(0.75)50.25)] + [(1.00) (1.00)] (©) (0.75) 0.25)] + {(0.50?0.75)) (@)_ (0.75) 0.25)] + [(0.50¥0.25)] Ifthe concentration of OH ions in the reaction Fe(OH) ;(s) = Fe** (aq) + 30H (aq) is decreased by ; times, then equilibrium concentration of Fe™ will inerease by : /2008) (a) 8times (b) 16times (©) GAtimes (a) times The dissociation equilibrium of a gas AB, can be represented as 2008] 2ABy( 2) 2AB(g) + By(g) ‘The degree of dissociation is ‘x’ and is small compared to. 1. The expression relating the degree of dissociation (x) with equilibrium constant K, and total pressure P is : @ CK/P) ) QK/P3 © @K,/Py2 @ (K,/P)2. 4 15, The values of Kp, and Xp, for the reactions NH vez (a) 2008] and A===28 Ad) are in the ratio of 9: I. Ifdegree of dissociation of ¥ and 4 be equal, then total pressure at ‘equilibrium for (a) and (b) are in the ratio: (a) () 1:9 (©) 36:1 @ ist ‘The value of equilibrium constant of the reaction HI(g) = PLS, is8.0 2008) ‘The equilibrium constant of the reaction Hy(g)+ L(g) 2HI(g) will be: 1 1 f@) 16 OG 1 © 6 @ 3 The following equilibrium constants are given Np+3Hy===2NHy:K, (2003, 2007] Ny +03 ==2NO:Ky Hy + $0), 0:K5 ‘The equilibrium constant for the oxidation of 2 moles NH, by oxygen to give NO is 2 2 KKS KiKs @) <2 (by “203 fa) a (b) Ky Kuk KK} © “ky Or’ For the reaction (2006) (CHy(g)+203(g) = CO, (g)+2H,00), AH=-1708kJ mol! Which of the following statements is not true ? (a) The equilibrium constant for the reaction {CO} (CH, ](02P° (b) Addition of CH,(g) or O,(2) at equilibrium will cause a shift to the right (c) Thereaction is exothermic: (d)_ At equilibrium, the concentrations of CO,(g) and H,0()) are not equal is given by Ky = 16. CHEMISTRY K, and K, are equilibrium constant for reactions @and (iy NyQ)+ 0, (g) == 2NO(g) i) 1 1 ‘i NO(g) SF N2(8)+ 5028) alli) ‘Then, 11989, 94, 2005] f @ &, A) 0) KK? 1 © Ke @ Ky=(K” Value of Kp in the reaction MgCOj(s) > MgO(s)+ COz(g) is @ Kp=Peo, ©) Kp=Peo, f2000) Peo, *Putgo Puugcoy Feo, * Paugo. Pugcos Piso, Feo, Paige For dibasic acid correct order is Ka Kay © Ka =Key (6) notcertain If K, and Ky are the respective equilibrium constants for the two reactions Xe (g) + H,0(g) = XeOF,(g)+ HF) XeO,(g)+ XeF(g) = XeOF(g)+ XeOsF(2) the equilibrium constant of the reaction Xe0,(g) + 2HF(2) = XeO,F(2) + H,0(e) © Kp (@) Kp f2000) will be (1998) @) KK? (b) Ky. Ky (© KK; (@) KyK, If @ is the fraction of HI dissociated at equilibrium in the reaction, 2 HI (g) == H, (g) +1, (g), starting with 2 moles of HI, the total number of moles of reactants and products at ‘equilibrium are [1996] @ 2420 ) 2 () lta (d) 2-aEquilibrium 21, The rate constant for forward and backward reaction of hydrolysis ofester are 1,110"? and 1.5% 107 perminute respectively. Equilibrium constant for the reaction 11995] CHyCOOC,Hs +H* == CH;COOH+ CzH;OH is (a) 433 () 533 (© 633 (@) 733 Topic 2: Relation between K, Q and G and Factors Effecting Equilibrium 22, Hydrolysis of sucrose is given by the following reaction. 12020] Sucrose + H,O = Glucose + Fructose Ifthe equilibrium constant (K,) is 2 « 10! at 300 K, the value of A,G° at the same temperature will be (a) 8.314 Jmol 'K7 300 K x In * 10") (b) 8.314.Jmol K+ 300K x In(3 * 108) (0) -8.314Jmol"K7 x 300K In(4« 108) (@) -8314J mol IK = 300K * In <10" 23. Which one ofthe following conditions will favour maximum formation of the product in the reaction, 018} Ag(2)+ By(@)—==X,(g) ApH = kd (@) Low temperature and high pressure (b) Low temperature and low pressure (©) High temperature and low pressure (@)_ High temperature and high pressure 24. Consider the following liquid - vapour equilibrium, Pot} Liquid = Vapour Which of the following relations is correct ? dinG AH, dénP _ AH, aT?) RT? aT RT afnP_—AK, fob _~Ally © og © Ear 25, Which of the following statements is correct for a reversible process in a state of equilibrium ? 12015] 30 RTlog K 2.30 RT log K 2.30 RT log K 2.30 RTlogK 31 For the reversible reaction, pou} N,(e) + 3H,(g) = 2NH,(g) + heat ‘The equilibrium shifts in forward direction (a) Byincreasing the concentration of NH,(2) (b) By decreasing the pressure (©) By decreasing concentration of Nj(g) and Hie) (@)_ By increasing pressure and decreasing temperature. Fora given exothermic reaction, K, and Kare ‘the equilibrium constants at temperatures 7; and T,, respectively. Assuming that heat of reaction is constant in temperature range between 7, and Ty, it is readily observed that: (014) (@) K,>Kp () K,K, where K, is the equilibrium constant For the reaction 2Ba0,(s) = 2Ba0(5) + O42); AH = +ve. Inequilibrium condition, pressure of , is dependent on 2002] (a) massof BaO, (b) mass of BaO’ (©) temperature of equilibrium (@)_massaf Rad, and RaQ both In atwo-step exothermic reaction A2%(g)+ B2(e) 3C(g) == De) Step Step 2 Steps | and 2 are favoured respectively by 11997]32. 3 high pressure, high temperature and low pressure, low temperature (b)_ high pressure, low temperature and low pressure, high temperature (©) low pressure, high temperature and high pressure, high temperature (@)_ low pressure, low temperature and high pressure, low temperature The equilibrium constant for the react Ay = 24 at 500 K and 700 K are 1 * 10"! and 1 * 10-5 respectively. The given reaction is 11996] (@)_ exothermic (b) slow (©) endothermic (@) fast Standard Gibb’s free energy change for isomerization reaction 11995] cis-2- pentene == trans-2-pentene is—3.67 ki/molat 400K, Ifmoretrans-2-pentene is added to the reaction vessel, then (a) mote cis-2-pentene is formed (b) equilibrium remains unaffected (©) additional trans-2-pentene is formed (@)_ equilibrium is shifted in forward direction According to Le-chatelier’s principle, adding heat toa solid == liquid equilibrium will eause the (a) temperatureto increase 11993] (b)_ temperature to decrease (©) amount of liquid to decrease (@) amount of solid to decrease ‘Which one of the following information can be ied on the basis of Le Chatelier principle? 11992] (a) Dissociation constant of a weak acid (b) Entropy change in a reaction (©) Equilibrium constant ofa chemical reaction (@)_ Shift in equilibrium position on changing value of a constraint ‘Topic 3: Theories of Acids and Bases, Ionic 36. Product of Water and pH Seale ‘The pH of 0.01 M NaOH (aq) solution will be INEET Odisha 2019] @ 9 (b) 701 © 2 @ 2 Which of the following cannot act both as Bronsted acid and as Bronsted base? INET Odisha 2019] (@)_HS0, (b) HCO, (©) NH, «@ HCL 38 4 2 4B. 45 CHEMISTRY Conjugate base for Bronsted acids HO and HE are ory (a) OH and HF", respectively (b)_H,0" and F , respectively (©) OW and F,, respectively (@)_H,0* and H,F*, respectively Following solutions were prepared by mixing HC1+25 mL. “= NaOH 4 100mt™ Her 100mt™ Neon ™ 10 m0 pH of which one of them will be equal to 1 @ db © a © © @ 4 What is the pH of the resulting solution when equal volumes of 0.1 M NaOH and 0.01 M HCI remixed? [2015 RS] (a) 1265 & 20 ©) 10 (@) 104 Which of the following salts will give highest pHLin water? Pou} @ Ka (b) Nac (©) _Na,CO, (a) Cuso, Which Of these is least likely to act as Lewis base? INEET 2013] @ F () BF; © PF, @ co Which of the following is least likely to behave as Lewis base ? Pou} @ HO (b) NH, © BF, (@) OH Which one of the following molecular hydrides acts as a Lewis acid? Pot} (@) NH, () HO (©) BH, @ CH, Which of the following molecules acts as aT ewis acid 2009} (@) (CH), 0 © (CH) 3N (b) (CH), P @ (CH);BEquilibrium 46. 4. 49, 51. The ionization constant ofammonium hydroxide is 1.77 « 10-9 at 298 K. Hydrolysis constant of ammonium chloride is: 12009] (a) 6.50 10-1? (b) 5.65« 10-8 (©) s65x10'2 —— @) 5.65 10-9 Equal volumes of three acid solutions of pH3, 4 and 5 are mixed ina vessel. What will be the H™ ion concentration in the mixture? (2008 @ Lux104M — (b) 37*104M (©) 3.7*103M — @) L11x103M Calculate the pOH of a solution at 25°C that contains 1* 10°? M of hydronium ions, ic +#H,0*. 2007) (@) 4000 (b) 9.0000 (©) 1.000 (@ 7.000 ‘The hydrogen ion concentration of a 10-8 M HCI aqueous solution at 298 K (K,, = 10") is 2006} (@ 11x108M ——(b) 9525%10*M (©) 10%108M — (@)-1.0* 105M ‘What is the correct relationship between the pHs of isomolar solutions of sodium oxide (pH,), sodium sulphide (pH), sodium selenide (pH,) and sodium telluride (pH,)? 12005] (@)_ pH, > pH, > pH, > pH, (b)_pHy > pH, * pH; > pH, (©) pH, < pH, HC = CH> HOH> ROH (b) RCOOH> ROH>HOH> HC = CH (©) RCOOH>HOH> ROH>HC = CH (@_RCOOH>HOH> HC = CH>ROH Which one of the following compounds is nora protonic acid? P2003] (a) $0, (OH), &) BOW, (©) POOH), (@) SO(OH), In HS-, F, RNH, and NH,, order of proton accepting tendency will be 2001) (@) P>NH,>RNH,>HS- () HS->RNH,>NH, >I (© RNH,>NH,>HS (@) NH, >RNH,>HS-> 1 ‘A base when dissolved in water yields a solution «with a hydroxyl ion concentration of 0.05 mol litre! The solution is, 2000] a) basie (©) neutral or'e! Conjugate acid of NH 2000) (@) NHS (b) NH (NH, (@) NH Which of the following statements about pH and H" ion coneentration is incorrect? /2000] (a) Addition of one drop of concentrated HCI in NH, OH solution decreases pH ofthe solution, (©) Asolution of themixtureof one equivalent of ‘each of CH,COOH and NaOH has a pH of7 (©) pHofpure neutral water is not zero (@)_A.cold and concentrated HSO, has lower HT ion concentration than a dilute solution of H,S0,, Among boron trifluoride, stannic chloride and stannous chloride, Lewis acid is represented by 11999} (@)_ only stannic chloride (b) boron trifluoride and stannic chloride (©) boron trifluoride and stannous chloride (@)_ only boron trifluoride What is the H* ion concentration ofa solution prepared by dissolving 4 g of NaOH (Atomic =23.amu) in 1000mL? 1999) () 10¢M (@) 108M ‘The pH value ofa 10 M solution of HCl is (1995) fa) less than 0 (b) equal to0 (©) equal to 1 (4) equal to2Tovic 4: Ionisation of Weak Acids and ‘Bases and Relation between K, and Ki, 61. AL100°C the Ky of water is 5S times its value at 25°C. What will be the pH of neutral solution? (log 55= 1.74) INEET Kar, 2013] @ 613 () 700 (©) 787 (@ 513 62, Accumulation of lactic acid (HC3H503), a monobasic acid in tissues leads to pain and a feeling of fatigue. Ina 0.10M aqueous solution, lactic acid is 3.7% dissociated. The value of dissociation constant, K,, for this acid will be: INEET Kar. 2013] (@) 28*104 () 14= 105 (©) 14x 104 (@ 37*104 6. Aweak acid, HA, has a K, of 1.00 * 10%, If (0.100 mol ofthis acid is dissolved in one litre of water, the percentage of acid dissociated at equilbrium is closest to 12007) (a) 100% (b) 99.9%. (©)_ 0.100% (@) 8.0% 64, At2S°C, the dissociation constant of a base, BOH, is. 1.0 x 10%, The concentration. of hydroxyl ions in 0.01 M aqueous solution of the base would be 12005} (@) 1.0% 10° mol L-*(b) 1.0 10molL* (6) 2.0 10 molL! (A) 1.0107 mol L4 65. _onisation constant of CH,COOHis 1.7» 10°, Ifconcentration of H ions is 3.4 * 10M, then find out initial concentration of CH,COOH molecules 2001] (@ 34™104M —(b) 3410M (©) 68* 103M (d) 68* 104M, 65, Aqueous solution of acetic acid contains 1991) @)_CH,COO-and t* (b) CH,COO-, H,0* and CH,COOH (©) CH,COO-,H,O%and i” (@) CH,COOH,CH,COO™and Ht ‘Topic 5: Common Ion Effect, Salt Hydrolysis, Buffer Solutions and Solubility Product 67. Find out the solubility of Ni(OH), in 0.1. M NaOH. Given that the ionie product of Ni(OH),, is2< 108 12020) (@) 2*10*M ) 110M (© 110M (@ 2*10™M cs 1 RB CHEMISTRY The molar solubility of CaF,(K,,=5.3 «10-") in0.1 M solution of NaF will be INEET Odisha 2019] (@) 53% 10 molL* (6) 53* 10% mol Lt (©) 53% 10%mol (@) 5.3% 10% mol L* pH of a saturated solution of Ca(OH), is 9. The solubility product (K,,) of Ca(OH), is: 12019 @ 05 1015 (b) 0.25 10" © 0.12510 — @ 05 10 The solubility of BaSO, in water is 2.42 x 109 gL! at 298 K. The value of its solubility product (K.,) will be (Given molar mass of BaSO,=233 g mol!) @) 1.08 « 10- mol 2018 (6) 1.08» 10"? mol2L (©) 1.08% 10 moPL* (@) 1.08 * 10" mol°L2 Concentration of the Ag* ions in a saturat solution-of AgC,0p is 2210-4 mol Solubility product of Ag,C,04 i8:- 2017] "2.66% .10-17 (6) 45x10" (© 53%102 (@ 242~108 MY and NY,, two nearly insoluble salts, have the same K,, values of 6.2 * 10° at room temperature: Which statement would be true in regard to MY and NY? 2016] @) The molar solubilities of MY and VY, in water are idemtcal (6) The molar solubility of MY in water is less than that of NY, (©) Thesalts MY and NY, are more soluble in 0.5M KY than in pure water. (@)_ The addition of the salt of KY to solution of MY and NV, will have no effect on their solubilities, Consider the nitration of benzene using mixed cone of H,SO, and HNO,, Ifa large amount of KHSO, is added to the mixture, the rate of nitration will be 2016] (@) faster (©) unchanged (0) slower (@) doubledEquilibrium m4, TS. 16, Th B 80. 81 The K,, of Ag,C1O,, AgCl, AgBr and Agl are respectively, 1.1 10°12, 1.8 < 10-1°, 5.0 « 10°13, 83 10-17, Which one of the following salts will precipitate last if AgNO solution is added to the solution containing equal moles of NaCI, NaBr, Nal and NayCrO,?/2015) (@) AgCl (b) Agbr (©) Ag,CrO, (@) Agi ‘Which one of the following pairs of solution is not an acidie buffer ? 12015 RS] (a) HCIO, and NaClO, (b) CH,COOH and CH, COONa (©) HCO, and Na,CO, (@) HyPO, and NazPO, Using the Gibbs energy change, AG? =+ 63.3K, for the following reaction, Pow} Ag,CO, == 2Ag* (aq) + CO, (aq) the K.ofAg,CO4(s) in water at 25°Ciis- (R=8314 IK! mot") (@) 32% 10% (b) 80x10 (©) 2.9% 105 (@) 79% 107 Identify the correct order of solubility’n aqueous ‘medium: [NEET 2013p (a) ZnS>NayS> Cu. (b) NaS> CuS> ZnS: (©) Na,S>ZnS>CuS (4) CuS>ZnS>Na,S The values of K,, of CaCO and CaCO, are 4.7% 10-9 and 1.3 * 10° respectively at 25°C. If the mixture of these two is washed with water, what is the concentration of Ca* jons in water? INEET Kar. 2013] (a) 7.746 105M —(b) 5.831 x 105M. (©) 6.856% 105M — (d) 3.606% 105M The dissociation constant of a weak acid is 1x 10-4. In order to prepare a buffer solution with a pH = 5 the [Salt}(Acid] ratio should be INEET Kar. 2013] (@ 1:10 () 4:5 (10:1 @ 5:4 pH ofa saturated solution of Ba(OH),_ is 12. The value of solubility product (X,,) of Ba (OH), is 2012] (a) 3.3 «10-7 (b) 5.0% 107 © 40x 106 (@) 50106 Equimolar solutions of the following substances ‘were prepared separately. Which one of these will record the highest pH value? 202 (a) BaCly () AIC, © Licl (a) BeCl, Buffer solutions have constant acidity and alkalinity because Pony (a) these give unionised acid or base on reaction with added acid or alkali. (b) acids and alkalies in these solutions are shielded from attack by other ions. (©) they have large excess of H” or OH ions (@)_ they have fixed value of pH A buflér solution is prepared in which the concentration of NH; is 0.30 M and the concentration of NHL is 0.20 M. Ifthe equilibrium constant, K, for NH, equals 1.8 * 10-3, what is the pH of this solution ? (log 2.7= 0.433). ‘only (a) 908 b) 943 (© LR @ 8B In qualitative analysis, the metals of Group I can be separated from other ions by precipitating them as chloride salts. A solution initially contains Ag* and Pb?" at a concentration of 0:10 M, Aqueous HCL is added to this solution until dhe CF conceutration is 0.10M, What will the concentrations of Ag™ and Pb?* be at equilibrium? (Ky for AgCl= 1.8 10, Ky for PbCL,= L710) Pou) (@) [Ag*]= 1.8 «107 M; [PO*]=1,7 «10M (b) [Ag’]=1.8« 10" M;[Ph]=85 10M (©) [Ag]= 1.8 102M [Pb2]=1.7 «109M (@)_[Ag’]=1.8 10" M;[Pb]=85 «104M IfpH of.a saturated solution of Ba(OH), is 12, the value of its Ky is: Por] (@) 400% 108M (b) 4.00 107M (©) 5.00% 10M (@) 5.00% 107 MP ‘What is [H"] in mol/L of a solution that is 0.20 M in CH,COONaand0.10M in CH,COOH? K, for CH,COOH= 1.8% 107 pore fa) 35x 104 (b) 11x 10% (© 18105 (@ 9.0« 106 In a buffer solution containing equal concentration of B- and HB, the K, for B~ is 10, The pH of buffer solution is: " (2070) @ 10 7 © 6 @ 499. m1 B. g Equimolar solutions of the following were prepared in water separately. Which one of the solutions will record the highest pH? 2008) @ SC, (b) Bac, (©) MgCl, @ Cael, Which of the following pairs constitutes a buffer? 12006} (@) NaOH and NaCl (b) HNO, and NH,NO, (©) HCland KCL (@)_ HNO, and NaNO, H,S gas when passed through a solution of ans containing HCI, precipitates the cations of second group of qualitative analysis but not those belonging to the fourth group. It is because 12005] (a)_ presence of HCI decreases the sulphide ion concentration. solubility product of group II sulphides is more than that of group IV sulphides. (©)_ presence of HCI increases the sulphide ion concentration, sulphides of group IV cations. are unstable in HCl () @ ‘The solubility product of a sparingly soluble salt AX, is 3.2 « 10-1, Its solubility (in moles! Titre) is Pooay (@) 56x 10% (b) 3.1% 104 ( 2x104 @ 4x104 The solubility product of Agl at 25°C is 1.0. 10-™6 mol? L~®, The solubiliy of Agl in 10-*N solution of KI at 25°C is approximately (in mol L") [2003] (@) 10x 108 (b) Lox 10% (1010-2 @) 10x10" Solubility of MX,-type eletrolytes is 0.5 * 104 mol/lt, then find out X,, of electrolytes (20027 (@ Sx10 (b) 25« 10% (@ 1x10 @ Sx108 Which has the highest value of pH? (2002 (@ CH,COOK (b) Na,CO, © NLC (@) NaNO, Solution of 1 NNH,OH and 0.1 N NH,Cl has pH9.25. Then find out pK, of NH,OH (2002) @) 925 (b) 4.75 (395 (@ 825 101 CHEMISTRY Solubility of aM, salt is 3.5 * 10°, then its solubitity product will be pool] @_ 1.7%1016 (b) 1.7x106 © 17108 (@ 17x10? The solubility product of a sparingly soluble salt B4, is 4x 10", The solubility of Ba, is 11999) @ 4x104 (b) 4x10? 4x107 (@) 1x10 ‘The solubility products of CuS, Ag,S and HgS are 101, 10-4, 10-* respectively. The solubilities of these sulphides nee in the order 119971 (@) AgyS>HgS>CuS (b) Ag,S>CuS>HeS (©) HgS> Ag,S>CuS (@) CuS>Ag,S>HgS A physician wishes to prepare a butffer solution of pH = 3.58 that efficiently resists a change in pH yet contains only small concentrations of the buffering agents. Which one of the following sweak acids together with its sodium salt would be the best to use ? 11997) (@)._m-ohlorobenzdieacid (pK, =3.98) (b)__p-chlorocinnamic acid (pK, 4.41) (©) 2,S-dihydroxy benzoic acid (pK, = 2.97) (@_Acetoaceticacid (pK, = 3.58) The pH value of blood does not appreciably change by a small addition of an acid or a base, because the blood 11995] (@ isabody fluid (b) can be easily coagulated (©) contains iron asa part of the molecule (@ contains serum protein which acts as buffer Which ofthe following is most soluble? 19947 (a) Bi, $,(K,=1% 10) (b) Mn (K,,=7% 10"'*) (©) CuS(K,p=8» 10) (@) Ag, S(Ky=6% 1059). 0.1 Msolution of which one ofthese substances will be basic? 11992} (a) Sodium borate (b) Ammonium chloride (©) Calciumnitrate (@ Sodium sulphate.Equilibrium 103, In which of the following solvents, AgBr will have the highest solubility ? 11992) (@) 103MNaBr (6) 10°M NH,OH (©) Purewater @ 103M HBr 104, ‘The compound whose aqueous solution has the highest pH is 11988] (a) NaC (b) NaHCO, (©) Na,CO, (@) NHC. 12 (a) © [23] @ [34] [45 [ey 56 67] (a) 89. @) 13, w) [24 f [35 [i [a6 [ay @) 57. 68 | (a) ( [90 (by 14 @ 257 [36] [a7 [iby 38 | [oo [a (b) [90 15 (a) @ [26] @) [37] @) [a8 fia) 59 70 | (a) (a) | 92 © 16 @ P7f@ [38] © [a9 Ta) mn nfo 93, (a) Ole 28) [29 [ © [so] 60 |) [aa Pa] fa | [a8] [29] a [a0] @ [51 fa 62 | ©) [73 |) (| 95 @ fT @ oto fatto [21 63, 74 |e) (a) [96 Je |e [s]afarfa]orfeo)= ©) [207 [arf [42 [oy [53 [by 64 75 | (a) [97 © rf @ (a2 To [a3 To [54 To 65 76 | (b) (a) [98 =|5 ia T@ tsa Ta To Ts Ta 66 |b) L771) EZ) lL @ (Np +38; 22H: Ky ae No|[H> “oF ovr omenonns = Meh H,0] [i |[o> Applying (I-+3 Ill 1) we ill gt 2NH +50, A+ 2NO+3H0; an +40, 91,0545 NH? / [Na]lMa __[xoP_ | [rof [N2][92] ° [HF <(0.] Kak KDA, (@)_ Max. pressure of CO, = Pressure of CO, at equibrium For reaction, SCO) = S10(3)+CO4(2) k= .6 atm = maximum pressure of CO, volume of container at this s aT 0 P ai Since container is scaled and reaction was not earlier at equilibrium, n= constant, _ PV _ 04x20 “RT RT Put equation (ii) in equation (i) [° Ax 2 RT lore tie 3. (b) Equilibrium constant for reaction: [Product] [Reactant] ‘The value of K is very high so the system will contain mostly products at equilibrium, 4 (a) Ny(g)+0,(2) == 2NO(e) (Nop (N2](03] ” ai) K=16%1012=ll Nz +0; —=NO 2 +502 2 NO} py (N2]?[02)"" (© 280, +0) 280, K=278 (given) $0550; +40, K-| E) = JL =6 «102 ~ Varg 6" 10 (©) Ay +B, 2B; K, __lase [13] sy 3x42 32 (2.8%10~ 3x10 x 4.210 (©) For the reaction N(g)+02(g) = 2NO(g) [NOP {N2][02] For the reaction 2NO(g)+ 02(g)}== 2NO2(2) _ [02]? [NOP [03] For the reaction 62 1 NOS 2(g)+Oo(8) 1 x= N2F102] [N02] Loa Loo4 [N2F [02], [NOWO2}? _ [No}[02] [NO] [NO] [NO2] (@)_ 2C(s}+On(g) > 2COg(2) an =2-1=+1 K and Kare not equal I6An = 0, then (R7y! = 1 Eide K CHEMISTRY o PAG) * Bay 3Cg* Prey Mole ratio 2 1 301 Molarconcentration 11 0 0 att=0 Molar 0.50 0.75 0.75 0.25 concentration at equilibrium [CRIP] _ 0.75)°(0.25) ] (0.50)7(0.75) (©) Forthis reaction K.y is given by =(e")(OHF {-: [solid}=1]. If (OF) is decreased by j ‘times then for given reaction, equilibrium constant to remain constant, we have to inerease the concentration of [Fe] by factor of 4 ie. 4x 4 x 4= 64. Thus, option (c) is correct answer. To maintain the equilibrium (constant if ‘concentration of on¢ of the: product decreases by = ties then the concentration of anor prot ‘increased by the factor of (n), where x is the stoichiometric coeficient (b) For the reaction __. , 24Bp(g) = 24B(g)+ Bolg) initially 2 o 0 atequi 2(I-x) Es x ‘The partial pressure at equilibrium are caleulated on the basis of total number of moles at ‘equilibrium. ‘Total number of moles =2(I-a) + etx =2+x) 20-x) Pap xP where P is the total pressure, 2x x Pyp= SX? Py =a XP ab +2) #2” 4x) Since x is very small so can be neglected in denominator Thus, we get Pygy=(1-9)xP Q+x) PygaXxPEquilibrium 2 (9) Given reaction are rez andA == 2B Let the total pressure for reaction (i) and (ii) be P, and P, respectively, then Ky Ky 9 1 After dissociation, Ateg [Let 1 mole of ¥’dissociate with a as degree of uilibrium dissociation) Total number of moles= I-a+a+a=(I+a) x (a) Y4Z ae o o Kp -[) ax R, Ga ea (ice wi) Similarly for 4B Atequitibrium (i-a) 2a We have, 2oP, ) (l= 2) ,| P, % GS) ( ag Dividing (i) by (i), wezet Ky oR Ky 1 402. Ky 4 (given) @ (b). Given : Equilibrium constant (X,) for the reaction: 1 1 , Hig) > FHa(8) + Fh(@: K-80 To find equilibrium constant for the following reaction H,(g) +1)(g) = 2HI(g); rultiply () by2, we get 2HI(g) Hae) +(e: Ky ‘Now reverse equation (iii), we get H,(g)+1y(g) = 2HI(g): K 2 i) Gil) nt iN) ‘Equation (iv) isthe sameas the required equation i vig! (i), Anus, for equation (i) is Zi.e-option(b) iscorrect ‘When the equation for an equilibrium is multipied by a factor, the equilibrium constant must be raised to the power equal to the factor. For a reversible reaction, the equilibrium constant of the backward reaction is inverse of the equilibrium constant for the forward reaction. (@ Given, N>+3H; == 2NHy; Ky «(i Np +0) == 2NO; Ky Oo) 1 : H) +50) == H,0; Ky fil) We have to calculate 4NH; +50, ——+ 4NO+6H,0: K =? or 2NH; +50, — + 2NO+3H,0 (NOP [H,0P (0,7 Lxoy’ * TN ](03] For this equation, K x3 -_oF * UP 0}3 Now operate, X2-Ks” 1 (NOP {HOF [Ng Ite] INTO] [HP (0,7? (NHS? NOP [4,07 [NHS F (0.77 (a) First option is incorrect as the value of Kp given is wrong It showld have been, k Feo, Pen, *(Po,F (@)_Forreaction() [No? IN2103] and for reaetion (i) (@_ MgCO,(8) > Mz0(s)+CO2(e) MgO & MaCO, are solid and they do not exert any pressure and hence only pressure exerted is by CO,, Therefore Kp= Pog (6) In polyprotic acids the loss of second proton occurs much less readily than the first. Usually the K., values for successive loss of ‘protons from these acids differ by at least a factor of Wie, Ky > Kay HXS=H HX K,, HX ==H x K, (@) Forthe action Xek,(g) + H,0(g) == XeOF,(g) + 2HF(g) [XeOF [HET [XeFe [30] and for the reaction XeOg)+XeF,(g) + XeOF (g)+HeO,F,(e) [XcOFJLXeO5Fy | [Xe0 4 JIXeF] seul) For reaction Xe04(g) + 2HF(g) > XeO3Fa;g) +H0(2) os ela) K. m4 CHEMISTRY = X03 )[H20] [Xe0, ][ FY From eq. no. (a) and (b) K=Ky/ Ky (b) According to equation OHI — H+ Att=0 (2 moles) ° ° Avcquilibvim (2—20)moles amole ame Total moles at equilibrium=2-2a+a+a=2 mole (@ Rate constant of forward reaction (K,) = 1.1 = 107 and rate constant of backward reaction (K,)= 1.5 * 10° per minute. Equilibrium constant (K,) AG?+RTIn Q At equilibrium AG=0,O=K,, So, A,G°=-RTIn Ky A,@?=-8314 Jmol! K! x 300K «In 10!) @ A,@t BK — X{o,a=-110 ‘On inereasing pressur® equilibrium shifts in a direction where number of moles decreases i.e forward direction. ‘On decreasing temperature, equilibrium shifts inexothermic direction i, forward direction. So, high pressure and low temperature favours maximum formation of product. (@)_ Clausius—Clapeyron’s equation din _ AHy aT RT? () AG’=-2.30R7log K because at equilibrium AG=0 (@ Given reaction is exothermic reaction. Henceaccording to Le Chatelier's principle low temperature favours the forward reaction and ‘on increasing pressure equilibrium will shift towards lesser number of moles i.e. forward direction {@)_In exothermic reactions on increasing temperature value of K, decreases K,> Ky (Assuming 7 <1) (© Given, CH,COOH = CH,COO- +H"; Ky =15 "105 i)Equilibrium HON == HF ONS K,, =45 «10718 or H+ CN> = HCN; x - 1 2 Ky 43x10” From (i) and (ii), we find thatthe equilibrium constant (K,) for the reaction, (CN-+CH,COOH == CH,COO-+HCN, is Ail) Ky = Ky iy 108 1510 =! 108 =3.33x108 1g 3 (@) For reaction w proveed fiom right to let Q > kK (backward) (forward) .¢ the reaction will be fast in backward direction ie 7,> ry. ‘When = K., the system is at equilibrium O K. reaction proceed from right to left (©) Forthe reaction BaQ3(s) === BaO(s)+ 03(g); AH= He. Atequilibrium-Ky= Po, [Forsolid and liquids concentration term istaken, as unity] Hence, the value of equilibrium constant depends only upon partial pressure of O,. Further on increasing temperature, formation of , increases as this is an endothermic reaction, ©) ABO = AW == PO since the steps | and 2 are exothermic hence low temprature will favour both the reactions. In step - L, moles are increasing hence low pressure will favour it. In step 2, moles are decreasing, hence high pressure will favour it. (b) 4, = 2A Equilibrium constantis given by lar [4] Since the value given is very small, hence conc. [of products less Incas hie scaction is slow, (a) Ifmore trans-2-pentene is added, then its concentration in right hand side will increase. But in order to maintain the K constant, concentration of cis-2-pentene will also increase. Therefore more cis-2-pentene will be formed. K, ou. 39. 41. (@_ Solid == Liquid It is an endothermic process. So when temperature is raised, more liquid is formed. Hence adding heat will shift the equilbrium in the forward direction, (@) According to Le-chatelier's principle ‘whenever a constraint is applied to a system in equilibrium, the system tends to readjust so as to nullify the effect of the constraint. (@)_ HCl eannot accept H* therefore cannot act as Bronsted base. (©) When a proton is removed from an acid, ‘we obtain its conjugate base. H,0—H* +OH” HEH" +E (©) Meq ofFICI= 75x e115 Meg. of NaOH = 2sxbxi=s Meq, of HC! in resulting solution = 10 NF ENS ATTN 0 Molarity of fH Jin resulting mixture= +55 75 1 pH=—log(H" 1 =-toa[ 5 10 (@ geqofNaOH=0.1 * 7=0.17 geq of HCI=0.01 x 0.017 geq of NaOH g eq. HCL hence, resultant solution should be basic, hence from the eqn ==log 4.5 «10? pH+ pOH= 14 & pH=14-1.34=1265 (©) NaxCO, is a salt of strong base (NaOH) and weak acid (H,CO;). On hydrolysis this salt will produce strongly basic solution, i.e, pH will be highest (pH > 7) for this sotluion. Others are combination of2 B. BE 4. KCI=Strong acid + Strong base 50. neutral solution (pH~7) NaCl= Strong acid + Strong base > neutral solution (pH ~7) ‘CuSO, =Strong acid + wake base > Acidic solution (pH <7) (b) BF; actsas Lewis acid, (©) BF; behaves as lewis acid as it is an clectron deficient species. (©) Boron in B,H, is electron deficient (@)_ (CH); B = is an electron deficient, thus behave as a lewis acid. (@) Ammonium chloride is asalt of weak base and strong acid. In this case, hydrolysis ‘constant, K;, can be calculated as Kee Kya SI. 65x10 (6) [H,0}' fora solution having pH =3 is given by [HOP = 110° molesfitee [ [HO] 10%) Similarly for solution having pH= 4, [H,O]*= 1+ 104 moles Titre and for pHES [HO"]= 110 motes’ ites 2 Letthe volume of each solution in mixturebe IL, then total volume of mixture solution =(414DLS3L Total [H,O7" ion present in mixture solution = (103 + 104+ 10) moles ‘Then [H,O]* ion concentration of mixture solution 107 +104 +10 3 0.00111 M = 0.00037 M=3.7 «104M. @)_ Given [H,0"1 at 25°C [H,0"] [OH] 1x 10-M, 54, 10 55. (@)_Forasolution of 10° M HCI, [H"]=10-* [H"] of water = 107 Total [H"] = 10-7 + 10°8= 10 108+ 10°8 108 (10+ 1)=11 = 10% CHEMISTRY @) The solution formed from isomolar solutions of sodium oxide, sodium sulphide, sodium selenide and sodium telluride are H,0, HS, H,Se & H,Te respectively. As the acidic strengh increases from H,O to H,Te thus pH decreases and hence the correct order of pHs is pH, > pH, > pH, > pH,- (@) For an acid-base indicator ly H+ In it CTO) ye TD fH] 0") 6 = Ta] In + atoeky, + log lt) or log = log Ky, +log M8 [a7] Taking negative on both sides [Hitn} log Ky, login! eee {in7 or wecan write pH =pKyy +1 te PH= PK Hog log(H 1 ia OF Tog HS acl (© The higher is the tendency to donate Droton, stronger is the acd. Thus, the comect order is R-COOH > HOH > R-OH> CH = CH. depending upon the rate of donation of proton. pH = py, ‘The stability order of conjugate base is RCOO® > H-0°>R-0° >HCS Ce (6) B(OH); does not provide HI" ions in water instead it accepts OH ion and hence it is Lewis acid BOH)s +H,0 = [B(OH),) +H" (©) Strong base has higher tendency to accept the proton. Increasing order of base and hence the order ofaccepting tendency of proton is 1 < HS” < NH, (1) ‘Therefore the solution is basic 56, (b) Because NH, after losing a proton (H*) ives NH NH; +H,0 === NH +107 (Conjugate acid-base pair differ only by'a proton) 57. (b) CH,COOH is weak acid while NaOH is strong base, so one equivalent of NaOH can not be neutralized with one equivalent of CH,COOH. Hence the solution of one equivalent ‘ofeach does not have pH value as 7. Its pH will be towards basic side as NaOH is a strong ba hence cone, of OL will be more than the eon. of’. 58. (©) Because of electron deficiency, boron trifluoride and stannous chloride are lewis acid. Vacant d-orbitals are available with stannic Chloride, hence it can also accept pair of electrons and act asa lewis acid 4 59 (d)_ No, of moles of NaOH = 45 = [Molecular weight of NaQH=40} No. of moles of OH = 0.1 Concentration of OH” = 2 = 0.1 mol/L Titre As we know that, [H*] [OH~]=10-!* (Ht}-10-8 ([OH7]=107) 60. (@) Molarity (M) = 10M. HCI is a strong acid and it is completely dissociated in aqueous solutions as : HC1 (10) = H"(10)+Cr. So, for every moles of HCl, there is one H. Therefore (H'] pH=— log" 61. (@) Kyat 25°C=1 x 10-4 AL2SC K,=[H"[0H-]= 10-4 At 100°C (given) [H*] [OH-]=55 = 10-14 for a neutral solution Ur] = [OH] 2 [P=55x 10-4 or [H*]=(55 x 10-4) : log [H"] a (On taking log on both side = log [H*] =—log (55 x 10"! pH= ae log55+14log10) pH=6.13 Calculation of pOH in this question: value of pH and pOH must be same for a neutral solution. “Thus, pOH =6.13, ako pH+ pOH =-bog (55 « 10-4) © a= Ka = |e, f= 0.037 = fs (0.037)’ x0.10= 1.37 «10 * 4x04 (@) Given K,= 1.005105, for a weak electrolyte, degree of dissociation Kz fixto a= [Ke c Vo100 (@) Given K,= 1.0% 10° 100mol [BOH]=0.01M [on]=? a= \Ky7e 1x10"? = 1.0*105 0.01 Now [OH-]=e.0. =0.01 « 105 1 10-7mol L-" (©) CH,COOH —= CH,COO-+H* i, ={CHCOO“ 1H") «[CH,COOH] Given that, [CH,COO™}= 34x10 M K, for CH,COOH= 1.7 « 10S CH,COOHis weak acid, soin it (CH,COOH] is equal to initial concentration. Hence 3.4x104)3.4x10) 17x10 [CH,COOH] {cHscoonj=34%10x3.4%00 17x10 =6.8% 103M6. n (b) An aqueous solution of acetic acid dissociates. as CH,COOH+H,0 == CH,COO+HOT NaOH —+ Na+OH- Total [OH ]=25+0.1 =0.1 Ni] [OH]? (O.1P s=2x 108 Solubility of Ni(OH),=2* 107M (a) CaF, = Ca? + 2F ’ oo At eam. sO NaF —> Na+ B. ot o.1 04 Due to common ion effect of NaF, solubility of CaF, is further supressed. Therefore, the concentration of F- will be mainly due to NaF, Kyo} F), ™ (0.128)? 0.142501 Koy 53x10" Used es (On? ay? 23 OP mol Le (@) Ca(OH), —Ca?* +2087 f10-8) - x05 K y= [C110], =|] "UY =05~ 10° (2) Solubility of BaSO,= 2.42 10° gL! 2.42103 233 (1.038 « 105) = 1.08 10-!° moP L? = 1.038107 mol 7! o AgoC04(3) =: rae" (aq)+ 20% (aq) K,=[Ae'P (C07) [ag*]=2.2* 10 'M Given that: Concentration of C,0,2 ions, [cor] 2.2104 C,0F M=1L1x104M CHEMISTRY Ky=Q.2 1042 (0.1104) =5.324x 1071? (b) MY = |Mt+y- Ky=2= 62108 Voz s=787* 1077 mol L*! NY; == |N443Y~ K,.=5% Gs) =2754=6.2 x 10-3 - [seu y" ‘ 7) s=3.89 10+ mol L>! molar solubility of NY, ismore than MY in, water. (b)_ The presence of large amount of KHSO, will decrease ionisation of H,SO, that result in lesser ionisation of nitric acid and lesser ‘formation of nitronium jon [NO,*]. Hence the rate of nitration will be slower. (©) AgyCrOy Kp =[Ae*P [C107] =11 10-2 [Ag® Agcl Ky =[Ag*] [Cl-]= 1.8 «101? 4, L810 (el er) AgBr Ky=[Ag*] [Br]=5.0« 10-13 4153x1079 [ag] nT a Agl Kp =[Ag*] [PF] =8.3 x 10717 4) 8.31077 [Ag rH Itwe take [ Cr}? ]=(Ch-]=[Br-]= [0] then maximum [Ag*] will be required Ag:COy (a) Among the given acids, HCIO, is a very strong acid, completely dissociates ~. [HA] > 0 in this ease, hence cannot be used for acidic bufier. corEquilibrium 16, n RB (b) AG=—2.303 log K here K=[Ag'P [COP ]=K,, + 633% 10"3=—2,303 «8.314% 298 log Ky, 63.3 x10 log Kyy= ~~ Sq93,g 7109 Kg = Antilog (— 11.09)=8 x 10-1? (©) Solubility ofalkali metalis maximum among the following. Among ZnS (1.7 * 10) & CuS (8 107) ZnS has higher value of K,. (a) CaCO, —> Ca”* +00} CaC,0,—> Ca?* + C0} [ca]=xty Now, K,, (CaCO,)= [Cx] [COZ] or 4.7x10%=(e+ yx similarly, K,, (CaC30,)=(Co?*]{C3074] or 13*10%=(r4y)y On solving. we wet [Ca?*] =7.746 * 10-5 M- (©) Given, K,= 1x 10-4 pK, = ~log (1x 10-4)= 4 Now from Handerson equation [Salt] H = pK, + log [Salt] eee acid Putting the values Taking antilog {Salt}[Acid] (H*] [OF-]= 10! oe? Since, s [OH ]= Ba(OH), <> Ba*+20H~ sods x103m,K,=s-(2 =5x107 > K,=5x 107 (a) (AICI, LiCl & BeCl) )all these solutions are acidic due to cationic hydrolysis, whereas BaCl,,issalt of strong base (Ba(OH),) and strong acid (HCD, hence it will have maximum pH (@) Constuat acidity and alkalinity of bulfer solution is due to the unionised acid or base. Lets take an example of an acidie buffer CH,COOH and CH,COONa CH,COOH == CH,COO- + HT; CH,COONa == CH,COO™ + Na* when few drops of HCI are added to this butter, the H” of HCI immediatly combine with CH,COO™ ions to form undissociated acetic acid molecules. Thus there will be no H” ions to combine with CH,COO~ ions to form undissoeiated ace(ieacid' molecules. Thus there will be no appreciable change in its pH value, Likewise if few drops of NaOH are added, the OFT ions will combine with H” ions to form Lnionised water molecule. Thus pH of solution will remain constant (b)_ Given : (NH3]=0.3 M, [NH,"]=0.2M, K,= 18% 105, [salt] = py +k POH= PK +log yy [pK = -log Ky: pK, = log 1.8 10-5] ©. pK y= 4.74 02 pOH =4.74log 75 = 4,74 +0.3010-0.4771 =4,56 pH=14-456=9.436 ©) Ky=[Ag}[Cl] 1.8 10-19=[Ag*] [0.1] [AgT=1.8* 109M K, = [Pb] [CrP 1.7% 10°5= [Pb] (0.1 [Pb°2]=1.7« 103M.85 87. 99. (d) Ba(OH),(s) —> Ba?*(ag)+2OH™ (aq) pH= 120° pOH=2 [OH-]=10?M Ba(OH)) —> pa? +2 0H osx10? 107 [-. Concentration of Ba?" is half of OH™] K,,=[Ba?*] (OH P =[0.5* 107] [1x 10? P 0.8% 10% =5% 107 MS It @) pH=pK,t @ pH=p tog{ SH] log[ H* Jr be x, tog |S =] ‘Acid Salt log [1 ]= toe og | liga = 1.8% 10% x @ Ky= 10; K, =104 oF pK For the buffer solution containing equal concentration of Band HB pH= pK, + log 1 PH= pK, (b) The highest pH will be recorded by the most basic solution. The basic nature of hydroxides of alkaline earth metals increase as ‘wemove from Mg to Ba and thus the solution of BaCl, in water will be most basic and so it will have highest pH. (@ HNO, isa weak acid and NaNO, is salt of that weak acid and strong base (NaOH), (@) IV group needs higher S? ion concentration In presence of HCl, the dissociation of HS decreases hence produces less amount of sulphide jn due to common ion effect, thus HCl decreases the solubility of H,S which is suffisient to precipitate IP group radicals CHEMISTRY (©) For AN; Ky = or s=3 4 (©) Ky forAgi=1* 10% In solution of KI, I> would be due to the both Agl and KI, 10 solution KI would provide =104r Agl would provide, say =xT- (vis solubility of Agi) Total 1 =(10-4 +3) Ky ofAgl= (10-4 +3) x > Ky= 104 ta2 P asx is very small x2 can be ignored lo x= 10-8 , le (solubility) 10 (@)_ Givens=0.5 « 10+ molesL (et, —= Ae +24) > For MX, K,,=8 (2sP= 4st Ko=4= (05% 104 =420)25810-2 =05%102=5 210-8 {b) Na,CO, isa salt of weak acid H,CO, and strong base NaOH, therefore, its aqueous solution will be basic hence has pH more than 7. NayCO} +2H;0—+ 2NaOH +2H2COs strong base yak acid [Salt] Base] [salt] or py = POH-loB TB aso] but pOH+ pH= 14 or pOH=14—pH {salt [Base] or 0 (mot ty () POH=pK, +log z L-pHt- tog BE px, ou 14-9.25 log = pk, Boa PKs 14-9.25-0=pK, pK,=4.75 (a) M;S—=2M* + s— Solubility product = (2s)? (s)=4s? =4(3.5% 10) =1.7 «10-16Equilibrium m7. 100, (@) BA, > B+24 ss Solubility product = [s] [2sP=4s 4x 10-12 =459 or 9= 5104 (©). For Binary salts like CuS & HgS, solubilty, > seus = VL07! = 3.16 10, sigs = VIO jg For Ag;S—> 2Ag*+S? 2 Yous 10x10 =13. 5410718 +. The order is Ag,S> CuS> HyS (Sal [Acid] For acetoacetie acid 3.58=3.58 + log [Sattl Ac (@ plt=pk, + og SL Thisis the required condition for maximum buffer capacity. (The buffer system present in serum is H,CO, + NaHCO, and as we known that a buffer solution resist the change in pH therefore pH value of blood does not change by a small addition of an acid or a base. 101. (a) ForBi,S,. K=(2s).GsP 452. 275) = 10885 [Kon 108 For MnS. K,, os Jy M NH,OH. AgBr is less soluble in NaBr and HBr due to presence of common ion (Br). With NH,OH, AgBr will react as: AgBr(s)*+ 2NH,OH(aq,) —> [Ag(NH),]Br(aq.)+2H,0(/) Hence, the highest solubility with NH,OH solution. (©) NaCl is a salt of strong acid and strong base hence its aqueous solution will be neutral i.e. pH=7, NaHCO, isan acidic salt hence pH< 7.Na,CO, isa salt of weak acid and strong base. Hence its aqueous solution will be strongly basie ie. pH>7. NH,Clissalt of weak base and strong acid, hence its aqueous solution wall be strongly acidic ie. pH<7.Redox Reactions & Trend Analys' with Important Topics & Sul TTopie Name SubTopic [QNS.[Lopans.[Lop] ans. [Lop [ans.[Lop|ans.|Loo| Oxidation number_| oxidation number | 1 | © Disproportionation | “sPropertionation afa}a fo land balancing of redox F——2eton balancing of redox reaction a fa reaction E- Easy D- bifficut Topic 1: Oxidation and Reduction Reactions fa) Otot4 (b) -4t0+4 - (©) 0t0—4 (0) +4t0+4 1 Zn gives H, gas with H,SO, and HCI but not] 5°) The oxidation stateofCr in CrO, is with HNO, because 2002) [NEET Odisha 2019} (2) Zmacis.asan oxidising agent when it reacts @4 ) 6 with HNO, @ #2 @ 6 (b) HNO, is weaker acid than H,SO, and HCI 5 (© In elzctrochemieal series, ‘above | © Oxidation numbers ofP in PO}, of Sin s hydrogen and that of Cr in Cr,03> are respectively (© _ NO; isteduced in preférence to hydronium 2009) jon (@) +3,+6and+5 (by +5,+3and+6 2. Which ofthe following involves a redox reaction? © -3+6and+6 (@ +5,+6and+6 {@) ReactionofH,S0, with NiO 1997) | 7. The oxidation states of sulphur in the anions (b) Production of ozone from oxygen in the SO," 8,0," and S,0,* follow the order/2003] atmosphere by lightning @ s (©) Production ofnitrogen oxides from nitrogen oS and oxygen in the atmosphere by lightning ) (@)_ Evaporation of water © 3. The loss ofelectron is termed as /1995Y M , tio (@)_$,0,2> <8,0¢ ©) exidation ©) redaction & _A.compound coniains atoms of three elements (© combustion (@) neutralization Topic 2: Oxidation Number 4, What is the change in oxidation number of carbon in the following reaction? 2020] CH) +4CL,(g)—> CC1,() + 4HCI(Q) A, Band C. Ifthe oxidation number of dis +2, B is +5, and thatof Cis—2, the possible formula of the compound is 2000) @ 4,8C), () A\BC), © ABO, (@) ABC,Redox Reactions 9% ‘Topic 2 The oxidation number of phosphorus in pyro- phosphoric acid is 11999) @ 3 oH © 4 @ 5 ‘The oxidation number of chromium in potassium dichromateis 11988, 1995] fa) +6 (b) -5 (©) -2 (a) +2 Phosphorus has the oxidation state of + 3 in (@) Phosphorous acid 11994) (b) Orthophosphoric acid (©) Hypophosphorous acid (@)_ Metaphosphorie acid. : Disproportionation and Balancing of Redox Reactions Which of the following reactions are dispro- portionation reaction?” Porgy @) 2Cu' cu +Cu (>) 3MnO?"+ 4H’ + 2MnO;+ MnO, +2H,O a (9 2kMn0, —* > K,MnO,+Mn0, +0, (@) 2MnO,+3Min?*+2H,0 > Svin0, +4 Select the eorreet option fram the following: G@) (and (byonly—b) @), (and) (©) (@,(C)and(@) — (@) (@)and (only For the redox reaction Po1sy MnOy +C,0}- +H* + Mn?* +CO, +H,0 ‘The correct coefficients ofthe reactants for the balanced equation are MnO; C,03° HY @ 6s 2 () 2 3 16 © 8 16 @ 2 16 Consider the change in oxidation state of bromine corresponding to different emf values 5 asshown inthediagram below: 2018] Bro, —Y 5 pro; 2", B10. Brpeay Bo av ‘Then the species undergoing disproportion- ation is (a) BrO§ (©) HBO (b) Broz (@ br, 1s. 18, A mixture of potassium chlorate, oxalic acid and sulphuric acid is heated. During the reaction which element undergoes maximum change in the oxidation number ? pony @ Ss OH © cl @c When Cl, gasreacts with hot and concentrated sodium hydroxide solution, the oxidation number ofchlorine changes from : pony (a) zeroto +1 and zero to-$ (b) zero to-1 and zero to +5 (©) zeroto—1 and zero to +3 (@)_ zeroto +1 and zero to-3 The following redox reaction is balanced by which set of coefficients ? 11999] AiZn-+bNO3 +H” > NHS +28 30-+1Zn"* abe doef @1o1 0 1 3 4 ) 2 2 1 2 3 2 4 2 0 1 3° 4 @ 41 13 4 In which of the following reactions, there is no change in valency ? 11994) (a) 4KCIO, —> 3KCI0,+KCI (b) $0, +2H,S —> 2H,0+38 (© Bad, +H,S0, —> BasO, +10, (@ 3Ba0+0, —> 2Ba0,, Which substanée serves as a rédueing agent in the following reaction ? 11994) 14H + Cr, 03> +3Ni— 2Cr** + 7H,0+3NP* (@) 1,0 © Ni © H (@) Cro} ‘Topic 4: Electrode Potential and Oxidising, 2. Reducing Agents ‘The standard electrode potential (E*) values of APYAL Ag’/Ag, KK and Cr°"/Crare-1.66V, 0.80 V, -2.93V and 0.74 V, respectively. The correct decreasing order of reducing power of themetal is INEET Odisha 2019) @ Al>K>Ag>Cr (b) Ag>Cr>Al>K () K>Al>cr>Ag (@ K>Al>Ag>Cr21, Standard reduction potentials of the half. reactions are given below Fg) + 2c > 2F (ag); E°=+2.85V Clg) +26 > 2C1 (ag); B= + 1.36V CHEMISTRY The strongest oxidising and reducing agents respectively are (2012 M (@) F,andT (b) Brand Ct (©) CyandBr (a) Clyand, 2. The oxide, which cannot act asa reducing agent, Br,(l) +2¢ > 2Br (aq); E°=+ L.06V is 11995) © 20 (aq); E°=+0.53V (a) NO, (b) SO, (c) CC (d) Clo, 1 (d) | 4 (by) | 7 (b) | 10 | (a) | 13 | (b) | 16 | (b) | 19 | (b) | 22 |) Hints & Solutions 1. (@)_ Zine gives H, gas with dil H,SOJHCI but not with HINO, because in HNO,, NO,” ion is reduced and give NHNO,, N,O, NO and NO} [zn 2HNO, ——>Zn(NO,), + 2H}4 {early 6) HINO, + 8H—> NH, + 31,0 NH, + HNO, —> NH,NO, 4Zn+10HNO, —> 4Zn(NO;);+NH,NO,+3H,0 Zn is above of hydrogen in electrochemical series. So, Zn displaces H, from dilute H,SO, and HCL with liberation of H,, Zn + H,S0, > ZnSO, +H, 2 (©)(@)2NaOH+H,80, —>NazS04+2H0 (utralization) ° ° (&) 30, E24, 205 (not redox reaction) (© Ny +0, —H## 2 NO (redox reaction) oo 22 here oxidation of N, & reduction of O, is taking place (4) 1,00) + 1,0(.) (not redox reaction) (a) Losing of electron is called oxidation. 2 ‘st 4. (0) CHy(g)+4C1; (g) > CCl, (2) + 4HCI(g) Cha .¢ in oxidation state of carbon is—4 to +4 5. @)_ +6;s the most appropriate oxidation state of Crin CrO,, 6 POY =x+4-2) SOF =x 44-2) Cr F-20476: 2r=12;x=+6 7. (b) SO} — Sisin +4 oxidation state S,0} — Sisin +3 oxidation state $,03- -»Sisin--Soxidation sate & —(b)_ Oxidation number ofa compound must be 0. Using the values for A, B and C in the four ‘options we find that 4,(BC,), is the answer. (42)3 + (45) + 4-2))2=6 + (5-8)2=0 The structure of 80,2 and $,0,2> are symmetrical. Thus, both sulphur atoms are in same oxidation state. This isnot the case with $,0,2 or S402 ions. CheekRedox Reactions (@)_Pyrophosphoric acid H,P,0, Let oxidation state of phosphorus is x (4x1+62)x742x)=0 2. 2e=10 or x=45 (@)_Let.x= oxidation no, of Crin KC SOX D#(QXx)+7E2)=0 or2+2x-14 =Oorx=+6, (a) _O.N. of Pin HPO, (phosphorous acid) 3x1 +x 43%C2)=0orx=+3 In orthophosphoric acid (H,PO,) O.N. of P is +5, in hypophosphorous acid (H,PO.) itis +1 ‘while in metaphosphoric acid (HPO,), itis +5, (a) Inadisproportionation reaction, one specie ‘undergoes both oxidation and reduction Reduction 2 Cu’. Cu Oxidation —f Reduction tl gg 3MnOj + 4H’ —> 2MnOy + MnO, + 2H,0 Oxidation 4 2 (b) MnOy—>Mn**; Se~ gain a) 43 “4 C30} —+COp ; 2” loss ii) ‘Multiplying (i) by and (ii by 5 to balance 2MnOg +5 C30} —> 2 Mn?* +10 CO On balancing charge; 2MnOg +5 C,0}° +16 H* —> 2Mn** +10 CO, +8H,0 (©) Calculate £2, corresponding to each compound undergoing disproportionation reaction. The reaction for which E>, comes out + ve is spontaneous. HBrO—> Br, E HBrO—> BrOs F .595 V, SRP (cathode) 1.5V,SOP(anode) 2HBrO—> Br, + BrOy E? yy = SRP (cathode) — SRP (anode) 1595-15 0.095 V Eig, 20> AG <0 [spontaneous] 15, 18 a Reaction in (d) involves comproportionation or synproportionation. When two reactants, each containing the same clement but with a different ‘oxidation number, form a product in which the SMn0, + 4H L_____§_* Reduction It is opposite to disproportionation, +5, +6 +6 (©) KCIO; +H,C,04 +H 380, >K S04 -1 + KCL-CO, +H,0 i.e. maximum change in oxidation number is observed in Cl (+5 to-1). (>) Onreaction with hot and concentrated alkali amixture of chloride and chlorate is formed 3Cly +3 NaOH(excess) HO, “as SNaCl + NaClO; +3H,0 @) Zn Zn +207 fl) 86° +10H* + NOy> NH} 43H,0 ~-@) ‘operate eq. (1) *4++ &q. 2) * 1 Zn +10H* +NO3 > 4Zn?* + NH} +340 en ee ee (©) BaOz+H, $0, —> Ba $ 04+ Hy O} In this reaction, none of the elements undergoes a change in oxidation number or valency. (b)_ The clement undergo oxidation itself and reduces others is known as reducing agent. In this reaction O. N. of Ni Changes from 0 to +2 and hence Ni acts as a reducing agent. (©) Lesser is the reduction potential greater is the reducing power. Reducing power : K> Al> Cr>Ag (a) Fp is the strongest oxidising agent as it has highest reduction potential while I is the strongest reducing agent since it has lowest reduction potential be the oxidising power whereas the lower the value £ Higher the value of reduction potential, higher will 2. ‘of reduction potential higher willbe the reducing power. (©) Carbon has the maximum oxidation state of + 4, therefore carbon dioxide (CO,) cannot act as a reducing agent.Hydrogen WNC em ec Loe er eel Tey Topic Name Sub-Topic__[QNs.[top]ans.[Lon] ans. [top] ans.[Lop|ans.[Lop| Preparation ang properties of ita properties of hydrogen |___hydrogen Preparation and | hardness of water 1[a properties of water E- Easy D- Difficult ‘Topic 1: Preparation and Properties of ‘Hydrogen 1. Which of the following statements about hydrogen is incorrect ? 12016) @) hydrogen has three isotopes of which tvitium i the most common. (©) Hydrogen never acts as cation in ionic salts (©) Hydronium ion, H,O* exists freely in solution (@)_Dinydrogen does not act asa reducing agent When a substance 4 reacts with water, it produces a combustible gas B and a solution of substance C in water. When another substance D reacts with this solution of C, it also produces the same gas B on warming but D ean produce gas B on reaction with dilute sulphuric acid at room temperature. 4 imparts a deep golden yellow colour toa smokeless flame of Bunsen burn. A, B, Cand D respectively are 11998} (@) Na, Hy, NaOH, Zn (b) KH,,KOH,AL (©) Ca,H,, Ca(OH), Sa (@)CaC,,C,H,, Ca(OH)», Fe 3. Which one ofthe following pairs of substances on reaction will not evolve Hy gas? [1998 {@)_ Iron and H,S0, (aqueous) (6) Ironand steam (©) Copper and HCI (aqueous) (@)Soxtium and ethyl aleohol The hydride ion, H’, is a stronger base than the hydroxideion, OH. Which one ofthe following reactions will occur ifsodium hydride (Nall is dissolved in water? 1997] (@) HT (aq) +H,0(1) > H,07 (aq) (©) HE (aq)+ 11,01) > OH (aq) +H2(g) (© Hq) +H,00) > OH (aq) + 2H" (aq) + 2€" (@) He (@q)+H,00) reaction The ionization of hydrogen atom would give rise to [1990] G@) Hydrideion ——(b)_hydroniumion (©) Proton (2) hydroxy! ion. ‘Topic 2: Preparation and Properties of Water The number of hydrogen bonded water molecules(s) associated with CuSO,'5H,0 is INEET 2019 Odisha} @ 5 ) 3 1 2 The method used to remove temporary hardness of water is: Poy (@) Calgon’s method (b) Clark’s method (6) Ton-exchange method (@) Synthetic resins method