S.AB_ Physical Chemistry Equivalents of MnO,” = 1.6 5 4 S—m)=16%5 8.) NH, —> 2N+ 106 kde + COP —> [cHOM] i 8,02 —> 2802+8e D-6=2 2-6-4 2-12 Ew of $,0, MF (COPY N80) i.e, mBq of Cr0,2 = mEq of $,0, 45. @) FoC,0, — Fe" + 6,0, MnO,” oxidises Fe? and C02 both Fe +02 —> Fe +200, +3 Mn0,°-+ Se —> Mn SFeC,0,=3 MnO, 104 3M, 'N,O (Species wth oxidation number =+1 is N,) 46. Nop r4e— ltx6-0 We x5 Change in oxidation number=5-a=4->0= 1 47. Q) SFe®* Mn0,° + 8H°—> Se + 41,0 + Mn? 6F2" + C0, + MH —» 6Fe + 7H,0-+269" 48. (SOC, 21,0 —+ 1,80, -28C1 H.S0, = 2NsO1 2HCI = 2Ns0H 49. @) MnO,’ +5e — Mn (aide) Maj? +e —+ Ma, (baie son To)aL.40,=100 «SNM, 13, se = Sat 3 9 0) iting gt oe Pw ge el dase ‘51. (1) i. Withphenolphthalein indicator, NaHCO, does notreact with HC whereas with Na,CO, is 50% reaction, Vcr ail. (Half ie value of Na,CO,) i, With methyl orange indicator, NaHCO, reaets completely with HCI and with Na,CO, is 100% reaction, But y mL of HC is added affer Na,CO, has reacted upto NaHCO ic, half ite value of Na,CO, yey ~ Fall Fite value of NaHCO, + Half ie value of Na,co, ymb =x +xmL ‘Volume of HC required for completereaction of Na,CO, NyHi,+ CIP-+H,0 53, (8) 80," + H,O— $0, + 2H? +26 mq of salt= mEq of SO = (0.1m) 50=(0.1 2) 25 Sn-1 Meo $4. @)K,Slnk, 2 Nik, +2KF © 2KF + 25bE,—» 2KSOF, i) Bh 4 ‘i Adding Es, nd, gt K,Mofy + 286F,— 2KSbF,+ Ma, + $B) In.) e-+Mn— Min (nfuetor~ 1) Li ee (whicor= Plate (feo) Therefore, according 1 Eq, (iv) 2mol of SbF, = I mol of Mak, Eg of K,MaF,, lott, = 5-05 otha, $5, (4) FeSO, + FeS0,), + KMn0, —! Only FeSO, will be oxidised by KMn0,. mEq of FeSO, =mEq of KMn0, % 5 « 1001000 mol of FeSO, mq of FeSO, Pet Pe +e 1 eo" 56, (4)NO,° + As,S,—>As0,* + NO + SO, As,S, +20H,0—» 2As0,° +3802 + 40H + 28e M Exs,s, = Mr fctor = 28) (electrons lost 857 29 v4 D 57. (1) Me + Mn0,°—> MO,° + Min? Mn0,° #8H® + Se —> Mn?" + 4H,0 Mt +310 —s MO,° + 61 + (5-2) mg of MnO,2> = mEq of M" 1x55 [67x69] 5-2-3592 458, (1) InNaHC,0,, C0) oxidised 19 CO, and H® is neutralised Bw raate,0, (88 COP10%, (NalIC,0,)= 100.1 N MnO, =O1N $9, () FesC,0,) 2Mn0, 3C,0,2- Fe! isnot affected C0, 3,05 00. cro," + Hec0, tl” anne 61,02 + 14H® + 6° —> 208+ 74,0, Pop Fe He; 02-9200, +26 FeC,0,—> Fo" +200, + 3° ‘mEq of K,C1,0, = F&C,0, (0.08 6) « P= (065 * 3)» 200 = Pe 1200mL=12L 461, (1) Remember ita. fact: in neutral medium, K,MnO, (potassium ‘manganate) disproportionate as follows K,Mn0,—> KMnO, * MnO, (On balancing, we get 3Mn0 + 28,0 —» 2Mn0,° + 40H + MnO, fang = Festadyen tt, : a. 0) FMF He Mn0,° + 8H®+ Se —> Mn + 48,0 €r,0,2-+ 14H® + 66° —> 28+ 71,0 Using mole concept 28,0," 95,0)" +26" ‘Mn0,°=S,0.2- nq —mEq 02M «5 (msicton) = ER 10? 0 mL 64. @) 50-250} +8 36+ G0 — (C1089, 102° =8,08 qm 101 x3 40 mL* 025 +8 7= 266.67. 65, @) As.0,—4 2000)" +4 Se M0, —> Ma (evo e 22282306) cm As0s= iBq = mEq OA eid 200M oan Mowing” mo, 5-5 Solutions 5.49 66. (1) C102 = Sn (Sn®* —s Sn +26) m=6) TEg=1 Eq 1 2 mot = 4 mot om 2 I mol of Sn = 2 mol ofC,0, © 1 Jot of C0 67. (4) CWO, > x 35/2 = mBq CuCO, = mEq H,PO,=(0.5*3)*« ¥ 2 %q~33mL «0 pyeetons Fo20mexdw0s n es eaatess,) 10 (revo tge aw) Feber tomal=2 [Ft ore te] Wao ra) 100 Pao) 100 5, oT = Wrsoymo™ 2224 nx > %ofFes0,7H,0= 224 100%: 25 68, (1) Mu0, +1 —> 1, + Mi 1, +2Na,8,0,—> Na,S,0, +2Nal {mEq Na,S0, =(1 0.075)» 30) mq Na,S,0, = mEq I, = mig MnO, co, a2 > %Mn0,= 753% 70. (1) H,C,0, > 2C0, = 2H® +26 PY 82x51 “RT 0.082350 7 % 1000 = (1 «0.075) «30 1 FX IMEI 0, Lae 7° pag > Seem elt 7 Proon = 2.86 L TL Q)NaC,0; —_ KHC,0,H,C,0, mmol mmol be xxOtyx3=02%0 HL xx 24 yxd=O2 "SKM B - 72.) ‘n factor of H,C,0, (oxalic acid) =2 “a factor of KMaO, in acide medium = 55.50. Physical Chemistry mg, of KMnO, = 20% 0.135 = 10 mEq. of H.C,0, 5 02%2=10 + Mno2—> Fe! + Me ) (ofactor= 5) of F&* = of MnO Smole = 1 mol fs Fe + Cqok}—> Fe + 208" (factor ~ 1) (nfactor~ 6) by. of Fe" = Bg. of C0 1 mole =116 mot 61 = 1 mol Ratio of moles of Fe oxidised by 1 mol of MnO and | mol of COF~ 516 ma 2 2 # i Si80, + FeSO\NH,),S0, —>Sn + Fe (a factor=2) Cn factor =1) Fy, of Sn = Eq, of Fe (in FAS) V2mol = 1 mol Ratio of moles of St and motes of FAS = 12:1 fi, ‘n'factorof Mao =5 Fa. ofMn03 = Ee. of Fo in (FAS) VS mol = 1 mol Ratio= V2 5 Ws 2 0) i. NaOH will react with NaHIC,O, (a acid) (Cn factor= 1, one replaceable H® ion) Mv and Ew of NaHIC,O, ~ 112 még, of NaOH mF, of NAHC,0, WLOfNAHC,0, = m.fy. «1022 109 x11 248 ii, MnO? (= 5) will react with €,03-(0s reducing 2) 248 cof —+200, +2 Bw of AHC0,- 1122 = 568 in of NaHCO, =m, of MnOf = 100 mL «0.025 0 =10% 1056-056 Mi. of NalIC,O, Thus b= 0.56 76.) ma), mw au 036 Hencea:b= 224 4:1 ora =a Fg, of Na,C,04(r 2) + Ba 061460, = Fg oFMNO, 47-9) ink) x04 x5 =0sy, Since 1 mol of NCO, 2 Ban 1 ma oF, C,0, Ea) 12 Bg. ofNyC,0,+2 Ego FLC,0, “08, Eg.of MnO? 2+2-08V, 5V,=8L NaOH wl tt wth only HCO, (aid) 24° replace 24. of NOH (n= 1) V, (01)«02Mx1 (mole of H,C,0, 2-02V, > V,~10L Hence V, :V,=8:10=4:5 KMn0, eats wit bth NaHCO, (2) and KALCO, Hou 242-4) (cot —> 200, +26) Let moles ofNaC,0, 4 =24 Ea Letmole of KHC,0,HC,0,=b=4 Ey, Let volume of KMn0, = VL. £4, of NCO, + £4. OF KHCOg HCO, ~ Fa of KMn0, 2a+40=02N*V nL) ‘his 2a-+4b=02V © NaOH, (itis acid base titration). reacts with NalIC,O, (y= 1, one replaceable H® ion) and KH.C,O,. HC,0, (1 = 3, one replaceable H® ion in KHC,0, and two replaceable Hons in H,C,0). Volume of NaOH = VI. a, of NaHIC,0, + Bq of KHC,O,. Hi 4, of NaOH a+3b=O12NxV(inL) 2) ‘Tusa 36 0.12V From £4. (1) and 2) 4-006, and b=0.02V ora:b=3:1 FeC,0,),+Mn09+H°—» 2Fe!"+ 6C0, + H,0 FeC,0, + Mn08+ + H°—» Fe" +260, + ‘Toial Ey. of (Fe(C,0,), + FeC,0,)= Fa of KMn0,Solwons $51 79, @)20mL of MHCL Equimolar mixture of ferrous and feric oxalate (Le, 0.5 mol ‘of each) 05x6+05x3=4%5 moles of KMn0, == 0.96 0 mL of 0.1 M NaHCO, + 5 mL. of 0.2 MNa,CO,, (methyl orange indicated 100% reaction of NaHCO, and 1Na,C0,) (02M Na,CO,= 0.4 N'Na,CO, 21422-0115 80, (4) i. With phenolpbthalein indicator: NaHCO, does not react with HCL whereas Na,CO, reacts upto NaHCO, stage (50% reaction). Vy 1H, With mothyl orange indicator: NaHCO, reacts completely with HCl and with NajCO, is 100% reaction. But ym of HCl isaued after Na,CO, has teacted upto NaHCO), (i, re value of Na,CO,) ull titre value of NaHCO, + Half te value of _y ml ~ Full ire value of NaHCO, +x mL, Full ire value of NaHCO, = (yx) mL. 1, (1) 0.05 MNa,CO, =0.1 NNa,CO, (0.05 M NallCO, = 0.05 N NaliCO, 40 Lof 0.1 NNa,CO, = 40 mL of 0.1 N HCL (For complete reaction) =80 ml. of 0.05 M HC or $M reaction = 40 mi. of 0.05 M HCL ‘With phenolphhalein = x= 40 mL. ‘With methyl orange, y= 80 +40 = 120 mL. 9) =80mL 82. ()KOH + Na,CO, (mmol) (mmol) ria & Gx Deoxa xy = pais 1 H (1) +6 *2)~ x28 Sy-0Sands~0.25 GxN+O%I= 5 = Kol mmoles = 0.25 « 109 « 562-0014 g £83, (4) Letxand y are the mEq of NaOH and Na,CO,, respectively Phenolphthalein as indicator: 1 Im of NaOH = + mg of Na,CO, = mEq of HCL xt tala 5 5 = fx1x20=10 i) ‘Methyl orange as indicator: mEGNALCOW(ER) sr of HCI i) 106 Weight of Na,CO,= 8:10 x 38 = 0424 g 24 of Na,C0, = 2424 £N0,00, = 2524 «100-596 84.04), 85.2) 86.(1) 87.2) 88.(1) Since, phenolphthalein indicates conversion of Na,CO, into NalICO, only, hence, x mL, of HCI will be further requried to comert NaHCO, to H,CO,, So, total volume of HCI required to convert Na,CO, into HCO, =3-+x=2emL. aco, —Y» Ca0 + C0, Since 9% pay of 1g of 2CO,= 09 Weight of 2CO,~09 Miro CaCO, 100 Moles of CACO, = Males of C0,=93 102 co, + NaOH —> NaHCO, 910% mes $010 moles ‘Moles of NaOH left = (50-9) x 10 = 41 10% = Ey. of HC1= Ea, of S08 05x 7141x101 mk In presence of phenopitlen (NCO, + Na1CO,) 124. of Na,CO, = Bg. of HCL 2 gq = X00 06? “To00 0106 viornco, 22%. 10-106 NaOH +Na,CO, In presence of phenolphhatein; Fg, of OOH +12 x Bg, of Na,C0, = Eg. of HCL eerste 40°06"? “000010 ne ay 40 "106 ~ 10000 Afcr this MeOH is added 12 x By. of Na,CO, ~ Bg. of HCL ¥y9=2.5x 4 Dx: J 106 70000 ‘10 1000 106 Substituting the value of equation (1) ise 7s jo000 T0000 Brix 104 = x 154010 06 8 Phenolphthalein gives the end point corresponding to the reactions: (e., half tire value) [NaOH + HCI—>Nacl +110 Na,CO, + HCL» NaHCO, + NaCl mmoles of NaH + mmoles of Na,CO, = mmoles of HCI= 25%0.1M=2.55.52 Physical Chemistry Methyl orange gives the end point corresponding to the reactions (i fall titre value) NaOH + HCL NaCl + H,0 Na,CO, +2HCL— 3NaCI+ CO, + 1,0 ‘mmoles of NAOH + mmoles oF Na,CO, «2 moles of HC! mmoles of Na,CO, = 3-25 = 05 mumoles of NaOH = 25-0. Ratio of m.moles of NaOH and Na,CO, 0 0.1 2 ode 0) 128,03 —e5,02-426 (1, ik 66+ BOS —> BHM) Bq of KB, = 1676 mBq, of S,0,> = mBq of BrO,? Nxsomi= 2 a9? Ew 0167 3 676 Ne ge = STROH 9 19 y= 0U2N Teves ee 90.(3) 1 for $.0, Ty, CHO" and MnO are 1,26 and 5 spectively £4, of NyS,0,= Ey. of berated = Bg, of KMn0, + Eg. of C150, 002 «5 +005 x6 4 or Wx Noor =Msyo? ‘x03 “ Msx03 91.(1) Moles of pure CuSO, = 0.12 moles of Na,S,0, reacted with Since n;for both CuSO, and ,0}° 92.(3) mmoles of KI= 50 0,04=2 Im.Eq of Na,8,0, reacted with 10 mL solution = 20 25 « 103 = 50% 109 m.Fq of fet unreacted in 100 mL solution 100 _ 10 = 30% 103 x 00 <9 mmoles of which ects wth CaCO, 2c + SI» 20ul + 1° mumoles of Cy =215 «15=06 Mir of CaCO, ~ 1235 Wei of CuCO, = 06 10° 1235 = 0.0741 078i 01 98.64) Iy+As0.2+2H,0—m HAsO} +20 +34 m.. of HAsO, (in SO mL) = mEq fy #3500523 sof uco,, 100-741 negara, nasniease 22-115 Mv of HASO,= 1 +75 +32=108 g Wi of HASO, in sample 75/2 « 108 x 10° =0.945 945 oo + 100 = 25% 94,(1) 1, +2Na,S,0, —> 2Nal +Na,8,0, ) mmoles of Na,S,0, consumed =15x04=6mmole mmoles of; consumed=3 mmole Sly +6NsOH— SNal + NalO, +3H,0 iy mmol of I reacted with NaOH. 30253 2 ‘Total mmole of consumed in the reaction Gand (i)= = 12 mmole +12=15 mmole iow 95.4) n, for Cr,0,>-and MnO = 6 and 5 respectively Ths Ev of C0, = 2386-49 By of KMn0, = 1585-316 REF FR, HO mE Lette mas oF mas of MIO, = (05-28 (x 5-2 Molarity off Fr SSE. 15001 x10 or x= 00732 2 Wot K,Cr,0, = 297 x 109 = 14.68 96.(4) mmoles of HCI=20 «0. 1 for MgO =2 mmoles of MgO reacted with HCI=22=> 1 Mf of MgO =40 g i of MgO present | x 40 mg 125 % 97.2) Total mEq. of NaOH taken = 20 mg, of H,S0, =m. of NaOH reacted = S202 250-10 m.£g, of NaOH reacted =20~Solwions 5.53 (NH),S0, + 2NaOH ——> Na,SO, + 2NH, +211,0 mmoles of (NH. ),SO, reacteed Mwrof (NH),S0,~ 132 8 Wi of (SHJ,80,= 5 « 109 « 132 Precentage of (NH,);S0, in sample 0.66 $e « 100 98. (4) MwofC,02-=24+64=86 8 Mwof 07° =8672=43 g(n,=2) my of C02 = m.Bg. MnO§ (n= 5) 25 1090 mx 0.01 Mx5=45 5 45x43 1000 0.193 ¢ 0.193 03 99.(2) mfg. of NH, reacted with HNO, 15x Ob 20.0.1 = 16 of oxalate i % 100= 64.59% GN in the sample 100. (4) m.B4 of FeO = m.Eg. of KMn0, 255% 100 0.25%100%5 _ 7 mmole of FeO (n= 1) = Total m.£g. or mmole of Fe? = 1000 «0.1 <6 = 600 (feom FeO and Fe,0, after reaction with Zn dust) mmole of Fe from FeO, = 600-125 =475 a7 mate ofF,0, = 92 2 Mw of FeO =(56-+16) 8, Miv of Fe,0, 135 tog 12556116) 000 mot Fo, = t 35g > “1000 38 se0- Gite ws 101.2) mz. of NCO, = mL OF KN, acted Mot Feo=. ‘Toul mg. of KMnO, excess m.£g. of KMnO, reacted with H.C,0, 45 x 0,02 x 5 100.1 x 1000 x 2 i Wangea04 = 0.1675 8 % purty of Na,C,0, in sample 0.1675 IS x 100-83.5 102.) 103. (1) 104.) 105. (4) 106. (1) 107.4) 108.3) [ce 301+ Bh» 58° + r0,2+31,0 0 G8 +0, +3€,07 —> BP +600, +3H,0 2) 10 manole of Bry produce (1013) mmole BrO® m.moles of | (CAC, 0, required = 103% 3= 10 Mow of C2C,0,= 128g IW of CAC,0,= 10 10 128 10x107 x128 2 2,(H9]= 102M, 2 gana! purity > 100 = 64 05107 40x 10° 10" mL. = 200 ppm ie w Pn Po = $02" (rom Na,S0,) —> PSO, Moles of Na,S0, equred = moles of Pb ions ~ o3ss/142 ~ 0.0028 [Pv] =o.0025050=5 «109 Moles of BaSO, =1.20233.3 12 Moles of My(S0),= Fat = 1.783 «109 Mi of M{SO,), = 0.596 1743 10° 2M +96 3) = 0.596 M=269 Moles of H,S0, = 0.1; mol of KO! Moles of H,SO, used in first reaction 0. 2 “oa 25 674 Mote of, produce= $4 = 023 “Moles of H,O, used in second reaction 03 3x05 ‘Total mole of H,O, consumed = 0.48 Molarity of H,0, = 0.4510.15=3 M Volume strength = 11.2 «3 =33.6 volumes Mole of 0, ~67.2/22.4 = 3 mole 30,20, api lle of Ozone formed = 215 3 =0.3 mole Mole of Ozone formed = 215 x 3 = 0.3 mol Mi.of Ozone formed = 0348 p= 14.4 8 Na,CO, + 1,80, —> Na,S0,+H,0+CO, Moles of CO, formed = moles of NaCO, reacted = 5,3/106=0.05 Volume of CO, formed a 1 atm pressure and 300 K 0.05 « 2463 = 1.2315.54 Physical Chemistry 109. 2) m.£4. of Ba(Mn0,), = m.£9. of 0, (m= 33.60 WISTS x 10 « 1000~3 x 128% 2; W=28.125 = wan x 100 8125/40 x 100= 70.31 110. (1) Ore of iron is Fe,0, which isa mixture of FeO + Fe,0,. InFe,0,, Fe isin +3 state which is reduced to +2 state (Pee — > Fe) (ln FeO, Feis in =2 stat) Fe in +2 state (from FeO and Fe,0, )is equivalent of MnO, MnO,” + SFe* + H® —> Ma + SFe®* + 1,0 mEq of KMnO,~ 50% xs 50 =SmEq = Smkg of Fe = 5% 107 «56g of Fe or Fe = 0280 3* 56 "= (3 * 56+ 64) g of Fe,0, 168 g=232 g of Fe,0, % of Fey0,= 20232 111, (2) MwrofK,CO,~ 392+ 124.48~ 138 mol! =55,20% svotk,c0,= aoe My of Li,CO, Bw of Li,cO, LetrgofK,CO, and (05 ~») got Li,CO, ti K,CO, +m of LC, = mE of HCL 5 05x (9S )x0m M+ 605=3) 30025 x37 ~~ 1000 00.28 300.2569 3; 1000 x05 MS~19,14~32r 32e= 15.36 and x =0.48 wot K,Co, ~ 248%100. %ofLisCO, 12. @) 6Br: +1201 —> 108? +2810,° + 610 SomLIAS™ 45 mL AS 6 na = 2 ml, (6+ 05)= 4434505 mm nO, snimel B:0,° = 60 Bry? + 3s)" + 6H® + Br? + 3As* + 3H,0 1 mmol BrO,” =3 mmol As 6:0 mmol BO,” = mmol As (oie =28-nm) 5 113, (DM + Mn0J—> MO,° + Mi Mn0,° 8H + 5=-—> Mn” +480 MP4 3105 MO? +6419 + (5-292 mg of Mn0,2-= mg of 1x52 [167*(6-2)]9S-2-33402 114, (DN; le I ol ‘i formed = 2 mol but dissolved in 0; hence pressure is duet Ny only. Hence, volume ofthe ask i 10 L since 10 10 i add 1 pp 3008 ar 1, (2) 1 mot KC, is obtsind from 2 mol of FeC#0, 025 mol KC, iabaned fom =0.50 mo of FCO, (100% pure) 1.00 mol Gs pure) 116, (In aide medium: mEq of KMnO, = mEq of HO (O01 *5)* 100%. 100 In basic medium: mq of KMnO, = mEq of HO, tn09 Bs vino (O01 1) «P= N% 100 «i rom equations (i) and (i), we got (O01 1) « ¥=(001 « 5) « 100-=> ¥=500 mL 117. (HCN + KMnO, —> CO, + NO,° + Mi 4 aco, (1g) =001 mol ‘mol of CO,=0.01 mol €N°+5H,O 90, +NO,° + 10H® + 106 Mnt,° + SH® + Se—yMn®*-+ 41,0 EN) +2Mn0,° + 6H —> CO, + NO, +2Mn* + 31,0 Tol CO, =2 mol MnO, 0.01 mol CO, = 0.02 mol MnO,’ 0.02 Mauos™ “35 = 08M 1000 MnO: + HCO, —> Mi (162) SOmLO.IN = mL = 0.01 N/30 mL 118. @) of M00, mBq of KMn0, = mEq of H,C,04] eosin = Excess mEq of H,C,0, in25 mL =001 «30-030 Excess mEq of H,C,0, in 250 mi mEq ofH,C,0, wed =$ 3 =2 ‘mBq of Mn,Solutions 5.55 Weight 37/2 Mat 1000 =2- Weight =0.087 g ost “5 <1” 19, Q) Referitustatin 3.13 120, (@) Methyl ed indiates is step onston of HP, 00, —= H®+11,P0, 43% (oat NaOH =H,P0, ny 01x 1 ¥,=0.1 = 1 100 Y= 100m. 121, (1)Metiyt orange indator indicates the st step ionisation oF 1480, 1,80, —* H° +1150, nT, oo-o(te=2#}ev-ary ‘cao = 11,80, NxM ANU O1x2* 7-02" 1x2 V,=200 mL 122, (2)Mecthy rd indicates the first stp ionisation of H,PO,. tes the second step ionisation of Bromothymol blue indi HPO, ie. H,P0,°—> H® + HPOZ- (n= 1) (W= at 1) First ease: When methyl red is added (change of H,PO,—» H,PO,° + H®)(n= 1) (N= 1) KOH=H,P0, NV aN 02% 1 «F-01100 ¥,=50mL. Second ease: When bromothymol blue is.added (change of #,0O,° —> H® + HPO) (n= 1) (N=M= 1) KOH =H,P0, Me NPs 02 1x F,=0.1 x1 «100 ¥,=S0mL. ‘oval voume~ $0 + 50~ 100 mL. 123, (4)Methyl red indicates complete ionisation of HCI (n = 1) and fist step ionisation of HPO, (n= 1). rst case: Ba(O1D, = HCL NVi~ Ny Py 01 *2«F,=0.1%1 «50 ¥,=25 mL, Second case: Ba(OH, = H,PO, (= 1) 04 x2 Y= 02* 1» 100 “otal volume= 100-+25 = 125 mL 124, (1) Methyl orange indicator indicates complete ionisation of HCI but frst steep ionisation of (8,80, —> H®-+ H80,° (n= 1) (Y= AP 1) First ease: Ba OH), = HCI MIN Ms 0.1 «2+ 100 = 200 mL. Second ease xOLeL Ba(OH), = H,S0, NVi~NaPy (0.12) 100 =02« Ly p= 100 mL. = 200 mL 128. (1) togv0s 4. V,0,+ 10° + 6e°—+ 2V2"+ 51,0 10 1000 => mEqV,0,— Bas" 5076 10> 1000 smmol (v,0,) = 920 = mmot v2" = 12 1900%2 is (V2 Vo +26 = mfictor = 2) Multiple Correct Answers Type Las HyC0¢—Asacid,n=2 As reducing agent, n= NaHC,0;: Asacid,n=1 As reducing agent, Mw F, M E604 lnentine rom = M iB, Hw (Feo laren (On reaction with KMaO, H,C,0, and NaH1C,0,: both are acting as reducing agents with sae n factor of 2 1. Se-+Mn0,° —> Mt Hk Be, —> 2Br0,° + 100 fil, 2MnO,°+ Bry +8H® —» 2M" + 2180,° + 24,05.56. Physical Chemistry soto) Mores M, iw(Br,) = 2 Butr)= 2 = 6) @) factor ratio (Mn0,°/Br,) 3.2.3) 1 (Se 3 [Ae > 2100} | “ ae-16--6| — 5807 10 Sx-40™-10 5x=30 ‘Add Eqs. (and (i, we get AsyS,— 2As0,> +580, +406 + Me] Gi) ews = ny for Cu,S, CuS and Ba(Mn0,), are 8, 6 and 10 respectively Bw of Cu,S = M8, Ew of CuS = M6 Ew of Ba(Mn0,);= M10 5.034) Statements (1,2, 4) are incorest Bw= Mw, Comet (a) (0) mott,708 sci asda vot 708 818 In both case, Bw of H,PO, 7 Stament sore (2) nottp0P asad 1 or2,sbase=1 Canes Inside median Bw of M0, = In basi median Bw of MnO, = In eal i ei Fw of MO, = Mw Maximum £ of M0, inbase mem In MgHt,, 0S. of H=—1 Comet (4) In H,0,,0.8.0f = +1 (OS. of His greater in H,0, 6,3) H,PO, + X(OH),——>AHPO, + 24,0 a (Since 2 H® are repleceable in H,PO,) (1) Ewotbase= Mw’? —@) Ewof HPO, 982 G) XHPO, + NaOH Moles of NaOH » 1 = Moles of SHPO, * 1 ‘Moles of NaOH (4) 21HPO, + OH, —> X{PO), +2H,0 Moles. 1 1 Moles of (OH), required = 12 7. ,2,3.4) () L%=1N 68% =4N, @ w= 4Ne M @) Lm =56-v" 68% =224-V" (4) Volume strength = 5.6 « N=5.6 2 M=112 «Mf 829) (o=2) 6) 20 mL *N,~40mL *N, ro) () meqor co «iy 20m * N,=40 mL = 5 @) 1NH,0,~56V :HONH,0, ~$6V NEN = Nh (Wy 1040 ~ 50mL) tox 1040» $2 =m 50 in) 10," 3 The volume stengh of ,0,=56%3~ 168 V 9.04.23) (1 ant2) 2H,0, -+2H,0 +0, 17 g/L of H,0, = IN~= 0.5 M~= 56 L of O, at STP “VS" of Hj0,~ 86 (@) $6 mL 273 K and 1 atm PVPs Ixs6= Wy 10.(1,3,4) When "VS"=56, M=05 ‘When “VS" = 28, then = Svea 36=25*Mo85g Wrof | lite solution =265 Moles of H,O ~ 180/18 = 10 (sd =265 gL) Wx100 _ 851000 Magi 34180 a4) Case I: reducing ant Fe does not oxidise 3¢,0° +60, +667 Px 0.1 «5 = 100 « 0.16 20 ml. nes Since Cr,0,? is reduced to CF, so H,O, must be oxidised tO, (Oxidation numberof rin Cr,0,>-is 6 and +3 in Cr" So, change in oxidation number ~ 3. Hence statements (2) and (4) are wrong. 13. 2,3) (1) Mn0,2. + 8H® + Sean? + 41,0 .1mod) mEq of Mn0,°= 0.1 » 3 Ret > Fete (05 mo) = mEq of Fe" = 05 @) FCO, Fe +200, +26 (0.166 mot) = mBq of FeC,0, = 0.166 * 3=0.5 @) ¢,0,° —200, +26 (025 mol) => mEq of C,02°=0.25 «2=05 (4) Cr,0,> being an oxidising agent eannot be oxidised. M4. (1,2) ‘The possible formula be A,B,C. ‘As compound is neutral, so x(=2) + (+5) +2(-2) > tSy—2e By hit and trial, we get:x= 1,» So compound is A(BC;), or ABC.) 15, 1,234) (1) mEq of Fe = 1x 5-5 mBq of Mn0,° = 1«5=5 ag, 18, Slutions_8:57 @) CxO + 6Fe + 1411 —> 268 + 71,0 + 6Fe 1 mol Cr,0,2-= 6 mol Fe 6) Find n factor of Cu, (8) Cut —9Cu** (notated reaction) +80, + 6¢ = I mol Cus: = rfactor of Cus= 6 mol > MnP » 28,0, + 5,02-+2¢(n= Bg of MnO,” = Eq oF S,0,> 5» moles of Ma0°= 1 * moles ofS,0,2 1 mol of 80,2 ~5 mal of MnO, (2) pit changes from 410 10 (acidic to strongly basic) © MnO, —> M02 (= 1) $,0,> 9250, + 86 (n=8) Eg of MnO,” Eq of 8,02 1 moles of MnO,” = 8 * moles of 5,02 tml ef,03-=! moto, Hence with change of pH from 4 to 10, will change the stoichiometry of reaction and also changes the product. (6) pl changes from 4107 (acidic to neutral medium) 3er#MnQ,° —> MnO; (n=3) $,02° —> 2H80,°+ 8 (= 8) Hence it will also effect the stoichiometry of reaction and nature of product (8) AtpH=7, 8,0, saxided H80,° ion 23,4) OH =| song tsi medion = Mn0,°—> MnO. (n-factor: 261141,0, —0,+2140+26 mfg H,0, =m of MO, * 1 sgn 10x(La1} tte as) NayC,0, and NaHCO, both reacts with H,O, as reducing agent ‘only. faetor for bath = 2) With 1,0, = Eq of Na,C,0, + Eq of NaHCO, 2x moles of H,O, =n, *2 +n) x2 rjes of 10, 204%) = (nth, 2558 Pia Chemistry 19. 20, a. With KOH: Only NaHIC,O, reacts with KOH as acid-base titration,» factor= 1 one H® ion) Eq of KOH ~ Eq of NalCO, 1c moles of KOH=, «1 moles of KOH = np :: Moles of H,0, and KOH are: (n+) and factor of NaHCO, with KOH and 8,0, ~ 1 and 2 factor of NaC,0, with H,O, and KOH = 2 and 2 2.4) Allhree ate seindieators ie, they donot need any indicator for 10° mol = 1 mmol Ko. M2 = mEq or8,02 (n=8) mg of C02 (n= 6) 1801607 y= 8 Yoxog- Smt sng oF8,0,-(n=1) 1n2xV V,-SmL mig of 8,0 (#=8) =m go Mn0,° (a= 3) 1e8=0103%¥ = mEq ofl, (n=2) 2 Mao o7 wes mL Also, Weight of K,C1,0,= 8x 724 x10" 6 03928 254 Weiaht of, ~ 174 10° 0127 Weigh of KMnO,~ 83158 2107 = 1264 es Since Cr,0,?-is reduced to CF, so H,O, must be oxidised 190, (Oxidation numberof Crin Cr,0,> is Gand +3 in Cr" So, change in oxidation number 3. Hence statements (2) and (4) are wrong. a2) (100 +2Mn0,° —> 2Mn?9 (n= 10) A Fe Re +e-(n=1) mq of (M0), = 100% Lx 10= 100 mEq of FeSO, = 100 « 1 = 100 mEq of FeC0, (n=3), Fo®s Fe pe €,0,°—+ 200, +26 100. Prax = 100 ~ mig of Ba(Mn0,), 2. mEqoFKCr,0, (n= 6)=25 «1 <6=150 A. mEq of C,02 5 x2* 1= 150, 209 mBq of H,$ = mEq of S* = mEq of AgNO, w [pi%pxtor] «0001 ewe 1)=38 1m (cay), Cu! —+ 3c +3e- (oxidation) Ph 5 H,P0, + Be (oxidation) 343-8-0 ass 4H,0 +0 +HPO,+ le +SH® 6) Reduction C0,-+ 6" + 14H® —> 27+ 74,0 «i Maltply equation () by 6 and equation (i by L1, net redox ‘equation is 6CugP +11C ae 8CuP* + 6HPO, +2267" + 31,0 fi, Number of moles of SO, used ~ 621,80, 12418 = 6250.2) Number of moles of CuSO, formed ~ I8CuSO, (= 18802) Number of mole of Ce, (504) formed = 154804), 33502) “Total number of SO,2 ion in reactant “Total number of $0 in in product = 18 + 33 = 51 Rest 11 mol of $0,2 ion inthe reactant react with 11/2 mol of ® ion to give IT mol of K,S0,, [Net redox reaction is {6Cu,P + 1IK,C1,0, + 62H,S0,—> I8CuSO, * 6H,PO, + S3H,0 + 11Cr,{S0,), + 1IK,S0, 24. 23.4) anbgotkoust~ x10! ~ 1090-2020 mt slon aan mEq of = 238,10 =2000 = 40120 mL solution Bg oF K,COyL= -E. x10" =2000 = 40/20 mts 100 Fi 1m of KHCO /L= {fpr 10" = 1000= 20/20 mi solution 2. With phenolphthatein: nntqof Kor! mEq oK,CO,=mE of HC 4 Ly, yee 20022 rtnet) Mg Am 3. With methyl orange: mBq of KOH + mEg of K,CO, + mE of KHCO, = mE of HCI 20+40+20-7*1N Ver 80 mL 4. With methyl orange after the first end point: 1 4 ofKCO, +m of KHCO, = of HI 20+20=1<1N Fug. = 40 mLSoltions 5.59 28. 2,3,4) 1 factor for RAWOH),COy isthe ttl positive or nezaive ann=4 ‘n factor for H,C,0, = 2 (2H® ions) te ios ta, mEq ofKAI(O1D,C0,~ mEq ofH,C:0, 100 mL. «0.2% Fasca04 Laxvmt zi 160 mi, Nswcnycoy ~02 «4-08 26. @) ‘ e106) 5 Ke16)+ 20, @ 3 yield fet a ial = Gr (SR = = joo = => mel nme + Loq — 100 mnt Smt) 10%) 18mmol——— 9 mmol) Geta 0%) fil, Zn(s) + H,S0,(ag) —> 2080 (aq) + H(e) 18 mal (yield = 10096) [Feemigeacany | 8am tnmoles of SO, required 2:02 Mx Vay =36 Figsoy= 180 27.2) 40H +211,0+x —+ x02+ 2 +4H,0]~4 x20 x x2 OH,0+ ge“ +NO,? —> NH + 31,0 96H roel e230 4X+7KOH +KNO, —> 4K,X0,+NH,t+2H,0 mEq of H,SO, (total) = 200 = 0.05 «2 (n factor) 20 mBq of NaOH = 10% 1.5% I (n factor) = 15 ‘mg of reacted H,SO,~ mEq of NH, 2-15=5 5 mmoles of NH, (n factor s Using mol concept! 1 mmol of NH, = 4 mmol of X 5 mmol of NH, = 20 mmol of X ab mot of x= 22,108 =20 NN he Aw of X= 100 Since n factor for X= 2 B10? + 106 SBF +2800, MM _toM _ 5a 2*0 6 3 mmoles of Br, = 18 1 = 18 Ew of Br, Sommatsoro,:~ 82-6 mEq of As” —pmbq.of BO,” =) a6 6+ B10, —> Be mfg of As" = mEq of BO, 45 «M2 cor) = 66 gi~ Baoan % . (4) Since 2 mol of HCO,” is present, So there should be one mole cach of CaCO, CaCl, and MgCl, to have equal hardness. Mw of HCO, = 61, ‘ppm of HCO,” = 61 <2~122.¢in 10° mL H,0 [iM of CaCO, = 100, fw oF CaCl, = 111, | mol of €2C0, 1 mol of CaCl, = 111 pom 1 mmol of MgCl, = 95 pan Hence, answer is (2) and (8), 4) Mw of CACO, + 40+ 1243 x 16= 100 g mot! Mw of Na,CO, = 46 + 60106 ¢ mot! 1. CaSO, + Na,CO, —+ CaCO, + Na,S0, 4) alt Fa = ™ sl Hh CaCl, + Na,CO, —+ CaCO, + 2NaCI i) ee fe yl {i100 ppm CaCO, = 100 g CaCO, i 106m. 100 pot in 10m. 100 Moles of Na,CO, required = Moles of CaCO, = 1 mol in 10% mt 1 10 108 mL (10L) 7 (oly % 10 mol in LOL, ‘Therefore, moles of Na,CO, required = 110? mol in 10L = 1107 « 106 g/10L~ 1.06 2 Similarly, for 100 ppm MgCO,: (Mi of MgCO, = 24 + 60 = 84 g mot)5.60. Physical Chemistry iy. MgSO, + Na,CO, —> MgCo, + “ moles ¥ MgCl + Na,CO, —> MgCO, + 2NaCl Ci) ™ “ ym vi 420 ppm MgCO, = 420 g MgCO, in 10° mL. Moles of Na,CO, required foles of MgCO, = 5 mol in 10° mL 10% 10" mL (101) io ao * 10 mol in 10L Moles of Na,CO, required = $ » 10? mol (10 L)* =5% 107% 106g (10L)" 53 g/10L 31.4) Since 2 mol of HCO,” is present. So there should be one mole «ach of CaCO, CaCl, and MgC, to have equal harnes. Mw of HCO," = 61, ‘pm of HCO,” = 61 « 2= 122 g in 10° mL. H,0 [Mw of CaCO, ~ 100, Mow of CaCl, = 111, Mie of MgCl, ~95 g mol] 1 mol of CACO, = 100 ppm 1 mot of Cac, 111 ppm 1 mol of MgCl ~95 ppm Hence, answers 2) and (4). 2.2.30 Moles of NalO, = 396198 = 2 (Mw of NalO,~ 198g) Reaction (1) 6H + 6" + 109 + 1° + 34,0 yo Hse® sof +30 +2043 10 3808 — P+ 380F aH 6B, all, 63, 8 Reaction 2) Or hs2e Ks Me" + 12H%+ 2109 —» 1, + 61,0 2108 + 1019 + 12° —> 61, + 61,0 1s 50.68 —» 34,431,0 was=5, 95-1 sa, sa 1. nfot109 in reaction 2)~5 2. Males of 1508 used in ration (1) for2 moles of 130-6 3. Moles of, produced = Moles of 1° used in reaction (2. 10 moles of © gives 6 moles of 2 moles of 1° = 6 0= 1.2 moles of |, 4.4 of102 wed in eatin (2)~ Eqivaens af ® Motes of 10? used * 1, of 10,9 = Moles of used af 1° 1x5=58q, 5x15 Bg 33.024) S10 +109 + 6H° —* 31, + 3H, moles of Kl wed imoles of KIO; used 1 ¥,=02L=200 mL, 2, For 0.006 mole H,S0, (0.012 mole H®), 0.012xs 6 Moles off produced 001=0.1%5, ¥,= 01 L= 100m 3, From 0.5 Lof KI solution (yy =0.05), 0.08x3 03 Moles off, produced 3 4 Valen fst R10, 5009 — Byrof KIO,» wis 34.3) 1 Cut* does no react with MnO,” on Only C,0,2 teats with MaO, on. Mn0,°= C02 (=5)(0=2) mEq =mEq rox 4 mE mq of ,0,-=2 mmoles of 0° 2 cut mEq w=) (2cu?* +21 —> Cush) 28,0, —9 8,0 +26) (er Cu*— ooh) (n M mBq of 8,02-= 25% x1 Bq of $05 ity mq of Cu" smkg of Cu**= 2.5 snmoles of Cu?* = 2. s Difference in mmoles of C,0,> and Cu? bw of cut ~ Atomic weight of Cu*Linked Comprehension Type Parageaph 1 1. @)Mn0," (acidic) 5,02 28,0 5,02 +26) 2. (1) Mn0,° =8,0,2 8,07 —> 2802 +8) (n= 8) (ts) woes] nfs 100 ml. «N= 100 mL 0.1 8 ye0s -—"_-osm incor 3. @) MnO,° =8,07 (8,02 — 2H80,°+8e )(n=8) (peo) or= 3 for = 100 mL * N= 100 mL 0.1 «8 7 wes 8g - u(t, 4 aur (ed M= 0.02 from Q. 1) Solve form: m= 0012 Paragraph 2 . @) Refer to Ilusration 3.52 Lit “Total mmoles BrO xh 6.) Tow BIO," = 202. = 1 1 Me ‘Tol motes of A0,° = 2x ee According othe balance equation for fist and second reaction $8e0,2-+ 200," +2H®— S8e0,2 +B, +H,0 Srmol 2 mnol 0 BrO,° + 3As0,° + H0—> BP +3450, +68 mol 3 ms “ Sminol of AsO," = I mmol of BrO,” in Eg. 11 = 1 mot orexcess =H ml of excess B10, mmoles of BO,” rected with Se0, in Eq () 11 mot oF 8:0,° reacted 1 . imal of A; 33636 [B10,° = As0,°1 Eg mB q= mEq + mol 2 10. @) 106" +2Mn0,° —> 2¥in 12.@ Soltions 5.61 1 mg excess mEq of B10,°= 1 mE . QoFBrO,° = EmEq 1 Hence, answer is (1) = 4 mi (D> gmea 7. @) mmoles of BrO,° reacted with SeO,2 in Eg (i) aoe % u = $Exs rfactor BO,” in E400) 3 ppgot Ho et ot 0} nat s 4. megetsiop = 8 (o mgarsiog 5 Mii of 0g 109» Be (evotscop = yer) or zy noses someon OF sax = 2x0 Paragraph 3 FeC,0,(n=3), (Fo > Fe +6, and C02 —9 200, +269) FeC,0,= Ba (MnO, !),= 00, C02 =(Mn0¢"), =C0. mEq mq mEq 20 ig = 20 mEq = 20 mEq 20x 10 11.) 2mnlotF0, 2 mmol of Ba(Mn0,), 24) ata BAL =natast 1000 mEq of CO, = 11200 mL. at STP 11200 20 mEq of CO, = 1200 2 F 8 rO To00 24 mL Paragraph 4 13. (1) 20. +26 > Cu,® [Number of es transfer per mol = Mw _ Mw Teacwor 1 Ewof CuSO,= 14. Q) CuS0,+KI— 1, 5,07 (6362) 02M 0 oF LOM 20u* +26 —> Cu, 241,26 2GiS0, AKI —> Cal, 2K 80,0 1,#28,0,7 921° + 8,0,> 2 mol CuSO, =4 mol KI= I mol Is mol 8,0, ‘mmol CuSO, 4 mal5.62 Physical Chemistry ‘Weight of CuS0,= 400 » 10 « 159.5 8 400 10 5159.5 100 ae 15, @) | mol CuSO, = mol $,0,? % CuSO, ~ 0% ‘mol KI 8 mol Paragraph 5 16. @) NaHCO, PBN, No reaction So, mEq of HCI =mEq KOH 50 x 0.2/100 ml. 50 % 0.2 10/1000 ml. = 100 mEq 100 x 10° x S6 gof KOH = 5.6.8 Weight of NaHCO, = (10-5.6)= 4.48 seotnaico,= #4 cima 17. @) Lets and mg ECO, ad NOH pt i ‘When phenoiptalin is seas inior 4 migoFNCO, +b ig of NAOH =m oF HCL 245 =20%04 «1-8 B = @ ‘When methyl orange is used as indicator ‘mEq of Na,CO, + 5 mEq of NaOH. atb=25% 04% 1=10 “i Solve fora and from Eqs. (i) and (i) -4nig= 4 t= =6m¢= mana hao of CO, NAOH=26= 13 1 @) Fran. 7 myo OH 6 0m) “ame mL Zerissemgt: wel 19, (1) From Q. 17, mmol of Na,CO, = 2 mmol (100 mL)" -20 mmol (1000 mL}! rigors 2i2gL! Paragraph 6 20, (4) The problem canbe solved simply by mol concept since» factor for both H,0, and Sn is 2. 2H® + HO, + Sa?" —Sn** + 2H,0 mmol of H,0, = mmol of S* = 100 m= 3. M~ 300 mmol 300 mmo of H,0, 300 «2 acto) mig HO, (00 mig = 0.6.69 ot 21, @) Moot, ily psens=136¢+ 104 = 04 mol of #0, Mol of H,0, left = (Mol oF 0, inital present ~ Mol of 0 reduced by Sn) 0-03 = 0.1 mol of HO, le Equivalent of 0, let= 0 = 2= 02 e9/100 ml. Ans. 1 2 22, @) INorEqL of 1,0, = 56 volume of O, at STP ‘(Volume of strength of H,0;) n= 92 510002191" of #,0, =36x2=112V 23, (1) 21,0, —> 2H,0 +0, 2 mol 1 mol 2 mol of H,O, gives I mol of O; 0.1 mol of H,0, gives 0.1 mol of, RT _0.1%0.082 300 P 7 246 L Paragraph 7 24, 2) As,S, + NaOH + H,O, > As0,* + H,0 + 80, Oxidation: As2*+ 160 —> 2450, + 8H,0 + de “ 2+ 24H —> 380, + 12,0 + 246 i) ASS5+ 4001 —> 2As02° + 380,2-+20H,0 + 28e- aD Red H,0, +26 —> 20H “wy Multiply Eg, (iv) by 14 and ad Eqs. i) and (v) to get ASS, + 1201+ 14H,0, > 2430) + 380,? +2010 i 2 3 20 (0) 25, (1) Initial mmoles of As,S,~ 0.4» 10040 Initial mmoles of NaOH = 5 100= 500 Initial mmoles of 0, = 6» 100 = 600 Balanced Eq, (8) shows that As,S, isthe limiting reagent ASS, +120H + 141,0,—> 2As0,> +380)-+ 2014,0 oo mae an UP me one me me Coed (sti) = w 2 ‘rs 0.) (1205 ‘volume a a = 26, 8) Ifa H,0, soltion i allowed to stan, it decomposes tO, and G0 1 Hos > 404504 — ofti0;] — Pe ‘Thames 00; ome = 40! ‘Volume of O, at STP = 20 « 103 + 22.4 L (1 mol of, at STP= 22.4 1) 448.Solutions 5.63 27. @) Mof H,0, lf 4 NofH0, as 0, left an 1s ail 0, IN of H,0, 6V" (Volume strength) = 1.7% 7x4=0452% is Anny 5 Paragraph 8 Bh () Fe FeyS0),—>3FeS0, Lm of FSO) (NHS, 24 2at 2a 241 myo of frie alum 968 mo! Fe($0,), mol of FeSO), 968 = 3x24 964 = 0.0075 mot of FeSO, 29, Q) IFCu were used in pace of Fe Soe ae ar aon Yt 2a ‘Note: Only FeSO, reacts with K,Cr,0, not CuSO, Since (Fe Fe* +e ybut Cu does not change. 241 2A1 spol of Fey($0,) mmol of FeS0, 968 = 0.005 mol of FeSO, Eg of K,C1,0, 30. @) mEq of FeSO, 3x21 1 (228) x10? = Lx oem tion x1 emt) v=15 m1. (Fo 9 Fe +0) (66 +609 200) 31, Q) mq of FeSO, «mks oFK,Cr,0, 2x241) 9 ol (22) = Leone v=s0m. Paragraph 9 32. (1) In first titration, both H,$O, and H,C,O, react with base, as ‘acid-base ittation. n factor Tor both i 2 due wo 2H® per mol in each ese. Letx= mEq af H,C,0, and y = mEq of H,$0,. mEq of H,C,0, + mEq of H,SO, = mEq of KOH, sy 20 0. +1 (ntact @ In second tration, only H,C,O, (being reducing agent) eats with K,Cr,0,, mEq of H,C,0, = mEq of K,C,0, @=2) (n=6) (02-4200, +26) 6+ C402 208) c mg oF H,C,0,= 50x51 x6 00 x= 1 mEq i) From Eqs. (and (i, we get x= mBq, y~1 mEq Weight of H,C,0,= 1 x 10745 (wot H.C, 00045 w/10 mL 45 1000 oe ‘Therefore, strength of H,C,0,=45 gL gl =45eL" Note: In the above reaction, H,SO, also reacts with K,CRO,, but inthe same reation with H,C,0, the mEq of H,SO, should not be added separately H,C,0,+K,Cr,0, + H,S0,—> 2c + CO, 33. @) mBq of H,S0,4)~ 1 Weight of H,S0,= 1 108% 49 evortis0,~ 2-9) $0009 210m Bosses 100 riche OB c,90,=49 9% 34 @) mga 0, -mEaofK.C10, Simm _ belo 10 Eq" Volume strength of H,0, Matrix Match Type 1. (@q) Mn0,°~Fe* @=5) @=0 TEq=1 Eq A amot = tot 1 mol=5 mol cus = Cy (=) (=6) 1 Eq=1 Eq {mol mol Cu,8=Mn0, (1=8) (1=5) 1Eq=1 Eq oon oo Tee el = carl ems tmot= 2 =16 5 (> G,0F =Fe fr=6) (@=1) 1 eg=1 84 ae aot = fa 1 mot=6 ol 2. (4-95) Mitre A: (NaOH +Ns,CO,) Ponsa ‘Wit pnp: (NAOH eas completely and 12 mq of NCO, 8) f a ‘with methyl orange (both react completely): ptq=bxt i) axl “i5.64 Pia Chemistry sove: £ =(-a),q=206-a) 2 ‘mmoles of Na,CO, (g)=2(6~a) 20 motes of Na,CO,(@) = SO =~ a) mmol (b> 9) Miature B: (NaHICO, + Na,CO,) With phenolphthalein: (NaHCO, does not react) Na,CO, react halt) $ =1° 1 mEqafNa,C0, s~2emEgofN,C0,= 2 = x mmol of Na,CO, With methyl orange (both reacts completly) rrp * ay re2e=y (4 @) r= 2s)mEq~ mmoles of NaHCO, (© p) NAOH in mixture Az Solve Eqs. () and (i) 3 ape Substitute the value ofg~ 2(b~ a) +b 3 apt 3xZo-a) =a+ ney Hb-a) = a+b 2p=a+b-3h+30=4a—25 4 By 280,° +e (a= 10) Bwor By ML 2=0 2e-12=2 G 2-10 o>p~ Br, 2800, = 1 26+ By, 2B (a=?) MM _ ow ou Br oBS Ig TS eo H,C,0,— 288+ (Bast factor p= it 2 NaiC,0,—9 uP + HP +6407 (Basiciy= 1) i= 1 aon ‘When it behaves as reducing agent (r= 2) for both 02 —+260, +26 w= M2 (for bot) aon Fo(C,07 )4Fe,(C,0,), EEE Mat + Fe + C0, O36) Since $ mol of Mn0,° of equal M of FeCO, and Fe(C,09) 6 ive, so moles ofeach = 25 1 Egat Mn0,°~ 1 EgofFeC,0, 4 mot = bmot ea Molsetv0,o= 253318 Similly, for Fe(C,0,)y (= 6) vor, 25x Total mo 055) factor for C02 ~6 Moles of €,0,2 for Fe(C,0,) oxidation = Noles of 0; be Fe(,0,) onion 25525 Total moles = 1.25 + 2.5 = 3.75 7 (ea) x8 + cuss EE Mat cuP*+ $0, Mise 0, fC eston= 25 Moles of MnO,” for Cu,§ oxidation = 2.5%. Total moles =3+4=7, aon factor for C1,07-~6, Moles af Cr,0;2 for CuS oxidation = 6.0% Makeso¢,0;+ Cu xdon= 602 80 7 ‘Total mol eon Mn0,° + C0,2> B25 Mn? + Cr +0, (r=) i=) Ms 140, eM, atin 208 6 Moles of 0, for C0, reduction = 2.0x5-=6 ‘Total moles =5+6= 11 Numerical Value Type L@ Moles of AgCl= motes of chloride 1.96 La (fw of AgCl = 143.5) Fag = 0136 (Mw oF ARC ) Wi of organi compound = 1.0 ¢ ‘Moles of onganie compound = 0/147 = 68 = 10% CCnlorine atoms in each moteule of organic compound 00136, bax107 2. (II) Fe 8, —> Fe, 0, + 80, Re ope, 428 a Total m actor 10+ 1= 11Soltions 5.65 £6.01 Fe co, fi. FeC,0), Fe*ion doesnt change. 3,02 —> 600, + 6¢ 6 (GO Cu," —s 300" +2¢ (n=2) > o=8) S450, +66 (1=6) Cu?* does not change only S* changes to $O, hence n 6 7. @) Refer to Istraton 3.13. SKI + 5H,S0,—>4K,SO, +41, + 1,5 + 41,0 aot) (mo) # ser oriio,- w= Me torr orto, = 12 MaiM 3x2 2 Le +2109 1, IP tae] 2109 +10 —> 61, Tmo! TOmal— Gmad Wl, + 28,0, —>8,02 +21 {ml of1\P=S ml? I5= 6 mol of 8,0,” mwa serno.-1" oS s asot0,-mll0, 10 28 e112 =004 5 (nr fctory* Y Beri =004% s(n facto) 000 m= 1 11, (H)10e° + 2Mn0,? —> 2M (n= 5) Eq of Mn0, x1 12, @)H,0,+ C107 —> [Cl er? + oF 2x=0 13. (2)11,0, +As,0, > A802 + H,0° (oxidation number of © 14, (10) Mivof washing soda = 286, Mw of CaCO, = 100 g mol! CaSO, +Na,CO, —> CaCO, +Na,S0, 0.0286 286)2 2) (0.0286 g Na,CO 10H, 10! = 0.2 mEq L0- o2mtaotNaco, = 22 melo x0, in = (0.1 10) «100 gin 10° mL =0.01 gin 10° mL. 18. @) Mn? MnO, + 26 de +0,—9 20,0 1 Eg of Mn? = 1 Eg of 0, (n=2) =a) 1 fimo =1 Ea 2 mol Mn®* = 4B of , 16. (2) 1,80, isa weak monobasi NaaxM 1, (A) EqoF KReO, = Eg oF MnO, 02% n=16Eq fi 02 Hence, there is an 8e-redction Re +ReO,” — Re “f) ah Oxidation state of 18, (2) First part: mmoles of Na,S,0, used = 842% 1 (nfactor)= 16 1, +2Na,S,0,—> 2Nal +Na,S,0, Imo 2mol rol of fused = mmol of Na,S,0,= 1-8 a i) Second Part: 31, + 6NaOH —» SNal + NalO, + 31,0 ce38 NaH = 300.1 x2 (factor) = 6 ‘mol of total NAOH = 300 0.1 > 1 (refactor) =30 ‘nmol of NaOH used = 30-6 = 24 inmoles of 1,80, 1 mmol of used = 4 mmol of NaOH use Loft, used = mmol of NAOH used 2 mmol ofl used ‘otal mmol of used = Part I+ Part IL 841220 mmol5.66. Physical Chemistry a ||| JEE Advanced Single Correct Answer Type 1. @)2Mn0,° + SC,02-+ 16H® —> 2MaP* + 10C0, + SHO = 2,y=52° 16 Multiple Correct Answers Type 1.3.4) (0) Inncutal or weak basie mem Mn0,° +3¢ —sNin0, (3) (@) In seongly alkaline medium Ma0,° +e° —+ Mino @)Imocidie metium Mn0,° + Se" —> Mn?* (n= 5) Linked Comprehension Type 1. @) Ist Method : tm moles of hypo = 025 » 48-2 mmoles of Cl, 0.25%48 2 6m mole mmoles of C roles of Cl mmoles of C20C, 6 ye So, molarity = M=026 M. Ind Method = 200") mEq of S,02 =025N «48 mL = 12 mEq of I, “mEq of 1° = mEq of Mx V (mL) =m motes _ mmoles __6 V(mL)— 25mL 2. (1) CaOCI, = Ca(OCY CL OCT: Hypochlorite ion, whieh is anion of HOCL Anhydride of HOC! = C1,0 =024M Numerical Value Type 1. (©) 30mL of 0.01 M [CiHH,0),C1}CI, = 2” ions ‘Number of C1” ions = 30 < 001 = 2=0.6 mmol motes of Ag® ions required = 0.6 mmol Volume =? Vx 01=06,- ¥=6mL 2. (8) Br, + 3Na,CO,—» SNalir+ NaBiO, + 300, 36 4. In neural or faintly alkaline medium: $,0}° + 51,0 —> 2180,° + 88 + 811°C" fae ‘or 8) fi, In basic medium 8,02 + 108H—> 2502 +SH,0+ 8¢ (n'fuctr Sin neutral or faintly alkaline medium: 38 +4 18+ Mn0,2—> MnO, + 2H,0 Cn fctor=3) Eq of Mn0,° ~ Ey of $,0,2°= Bg of 50,2. ) 2 = motes of,0,2 moles of MnO, =F moles of 5,0; S moles of Ma0,° =3 moles of §,0," Since 1 mol of $,0,> produces 2 moles of HSO,° +. 3moles 0,2 ~ 6 moles of HSO,° Hence the value of X86. 4.2992) Ca(OM), + (NH),S0, —> 2NH, + Ca80,211,0 (Gypsum) wR Weight fypmum omed= 12172 = 2064 Nici 61,0» aN, —> [NWN )C By My 38 5 Mass of [NNT JC, famed = 43292928 g Tonal weight = 206-028-2928 5.0.11) Volume of NaOH used at equivalent point 9 mL 109. of H,C,0, =m. eg. of NXOH Mn Neh 0.1 Mx ‘nj 5.0 mL= Ny 9 mL 04 *2* S0mL=N, x9 mL nye beat Noem 5 Normality of NaOH = Molarty of NaOH (Since "nj ~ 1), 6.6615) 2AL-+3H,$0,—> AL,($0,), +384 (8) ro) 34 Moles of Al = 2-02 270g mor Moles of H,S0,~50.0 mL.» 5.0 M= 0.25 From equation (2 moles ofAL~3 moles of 1,50, (02 moles of Al= 03 moles of H,S0, But moles of H,80, reacted = 0.25 ‘Thus, H,S0, is imiting eagen, 2Al_— + SSO, -> Al,($0), +3118) 02 mol 023 mel 025 mol MRT _0.25%0.0821 300 ? TOatm =618L,Solwions 5.67 7-(6 Insight alhatine medium, MnO,” redoes to MnO, MnO}'+3e"+21,0-» MnO +40H, cn? =3) Wis oxiiod tl, Io +26 C47 Bq. of MnO = Eq. of eq 1, = bmot= 1 mot 3m = meting} 22s of 8.(1.875) Fe MnO, +H" —> Fe! + Mn wf wes For 25 ml nil 9, of Fe" = mill eg, of MnO Mx25x1 = Sx 003x125 Sx003x125 4 ORES _9.03x25 For 250 ml [0.03 « 2.5] «250 ~18.75 18.25 « 103 = 1.875 » 107 9.18.75) % of Fe in sample = 1875 %107 x56. P55 100 = 18.15%Part 1 CHAPTER 2 Redox Reactions 24 22 23 24 28 26 27 28 29 2.10 211 Introduction Oxidation Reduction Electronic Concept of Oxidation and Reduction Oxidising Agent or Oxidant Reducing Agent or Reductant ‘Oxidation Number and State 2.7.1 Rules for Assigning Oxidation Number and State ‘Oxidation State of Oxygen in Different Forms 2.8.1 Oxidation State of Oxygen in Peroxides and Peracides 28.2 Oxidation State of Oxygen in Superoxides 2.8.3 Oxidation State of Oxygen, when it is Bonded to Fluorine Highest Oxidation State ofthe Group Element Stock Notation Fractional Oxidation State Concept Application Exercise 2.1 212 23 214 215 ‘Types of Redox Reactions 2.12.1 Combination Reactions 2.12.2 Decomposition Reactions 2.12.3 Displacement Reactions 2.124 Disproportionation Reactions Balancing of Redox Reactions 2.13.1 Oxidation Number Method 2.13.2 Ion Electron (Half Reaction) Method 2.13.3 Comparison of fon Electron and tion Number Methods of Balancing Equations Redox Reactions as the Basis for Titrations Balancing of H,O, as Oxidant and Reductant in Acidic and Basic Medium 21-232 21 21 21 21 21 21 22 22 24 24 25 25 25 25 26 27 28 28 28 28 29 212 212 212 213 213 24Concept Application Exercive 2.2 Exercises Single Correct Answer Type Multiple Correct Answers Type Linked Comprehension Type Matrix Match Type Numerical Value Type Archives Answers Key 219 221 221 225 227 228 2.30 231 2312.1 INTRODUCTION Chemistry is essentially a study of oxidation-reduction or redox reactions which involve transfer of electrons either between the atoms ofthe same molecule or between the atoms of different molecules. Redox reactions can take place either in the _28s phase or in solution or they may involve more than one phase {heterogeneous reactions) and occur both in inorganic and organic ‘compounds. 2.2 OXIDATION ‘Oxidation is the process of addition of oxygen or any electronegative ‘element or group or removal of hydrogen or any electropositive sFeCiag) (Addition of electronegative element) H,S(@) + Clg) "> 2HCKg) + 8%) (Removal of hydrogen) 4. K.Mn0,(aq) +0,(@) + 1,00) —2> knin0 aq) + KOH(g) (Removal of elestopositive clement) 2.3 REDUCTION Reduction is the process of addition of hydrogen or any cletropositive element or group or removal of oxygen or any clectronegative clement or group. For example a. Hyg) + Ch(g) —> 2HICI(g) (Addition of hydrogen) b. 2HgCl(aq) + SnC1,(eq) "> He,Cl,(s) + SnCl (aq) (Adkition of eletropositive clement) & Zn0(9)+ C19) "> Zm15) + COW) ‘Removal of oxygen) 4. 2FeChy(ag) + H,S(a) > Fecty(ag) + 2HCHa9) +869) (Removal ofeleetronegative element) 2.4 ELECTRONIC CONCEPT OF OXIDATION AND REDUCTION is process in which an atom ora group of atoms taking part in a chemical reaction loses one or more electrons, For example: 1 Mg—> Mg? + 2 Hh Fe > Fe he iii, $5 +26 ix. MnO? —> MnO, +e bb. Reduetion: [tis @ process in which an atom ora group of | atoms taking part in a chemical reaction gains one or more electrons. For example: i. Cl, +2 —> 201° Hh 2Hg? + 2¢—> Hy, fil, Zn? +26 —> Zn Is. Fe? +e Fe? 2.5 OXIDISING AGENT OR OXIDANT An oxidising agent or oxidant isa substance which supplies oxygen ‘orany other electronegative element or removes hydrogen oF any other electtopositve element. Altematively, an oxidising agent or oxidant is that substance which itself undergoes reduction in a chemical reaction For example, ©, Cly and O, in reactions (a) to (d) given in Section 2.2 are oxidising agents. Some examples of oxidising agents are MnO, (manganese dioxide), KMnO, (potassium permanganate), HNO, (nitric acid), and K,C,0, (potassium dichromate) & MnO J) + 4HCK{aq) —> MnCl(aq) + Che) + 2H,0() b. 2KMna0,(aq) + 10FeSO,(aq) + 8H,S0,(aq) —, MnSO,(ag) + K,S0,(a9) + SFe(SO,)s(aq) + 8H,0(), €. 1OHNO (aq) + 1{8)—> 10NO,(a) + 2H10 (aq) + 41,00) 4. K,C1,0,(aq) + 380,(g) + H,80,(aq) —, Cr{S0,),(¢a) + K,80,(09) + 1,010) 2.6 REDUCING AGENT OR REDUCTANT ‘A reducing agent or reductant is a substance which supplies hydrogen or any other electropositive element or removes oxygen of any other electronegative element. Alternatively, a reducing agent is that substance which itself undergoes oxidation in @ chemical reaction,