R K M ALI K ‘Ss JEE (MAIN & ADV.), MEDICAL + BOARD, NDA, IX & X a x Enjoys unparalleled reputation for best results NEWTON CLASSES in terms of percentage selection www.newtonclasses.net ELECTROCHEMISTRY |JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] JEE ADVANCED Single Correct Answers Type ve Rene Ce ae 1. The standard reduction potentials at 298 K for the © CITJEE 1981) Sova il recto Ben 2. Faraday’s laws of electrolysis are related othe lea): - ‘8. atomic number ofthe cation cra + D. atomic numberof axion 2H"(aq) + 2e ‘¢. equivalent weight of the electrolyte Fea) 42m) £20.70 speed ofthe eation (UT. JEE 1983) a Ue ee SBR UAA Ue tal) U1) ORT BTR) #RKMALIKSNEWTONCLASSES JEE ADVANCED PREVIOUS YEAR CHAPTERWISE SOLVED PAPERS [LAST 39 YEARS] Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0661-2662623, 3836600812, 0507613968 NEWTONCLASSES.NET.R. K. MALIK’S NEWTON CLASSES 3. solution containing one mole perlite of each Cu(NO ‘AgNOs; Hg,(NOs),; and Mg(NO;); is being electrolysed by using inert electrodes. The values of standard electrode potentials in volts (reduction potentials) are: ‘Ag/Ag’ = +0.80, ? Hg/Hig,”* = 40.79 (CulCa"* = 40:34, MgMg” = -2.37 With increasing voltage, the sequence of deposition of metals a the cathode will be a. Ag Hg,CuMg bi. Mg, Cu, He, Ag © Ag He, Cu a. Cu, Hg. Ag CIT-IEE 1984) 1. The electric charge for electrode deposition of one gram. equivalent ofa substance is a. one ampere per second }. 96500 coullombs per second € one ampere for one hour 4. charge on one mole of electrons (UTJEE 1984) 5. The reaction: U2H(g) + Agi) ‘occurs in the galvanic cel \.ARLARCIGs) | KCK soln) AgNO,(soln)|Ag b. Pt! Ha(g) IHICisoln) | AgNO,(s) [Ag € PLIHa(g) I HC\soln) | AgCKGs) |Ag 4. PCI Hy(g)KCI(soIn) | AgCs) [Ag (ITT-JEE 1985) ‘When a lead storage battery is discharged, a. SO, is evolved bb. Lead is formed Lead sulphate is consumed 4. Sulphuric acid is consumed (IT-JEE 1986) 7. solution of sodium sulphate in water is clectolysed using inert electrodes. The products atthe cathode and anode are respectively. (aq) + CT(aq) + Ag(s) b. OH, % 4. 0, SO, (IT-JEE 1987) ‘The standard reduction potentials £° forthe half reactions Zn=Zn"* +267) E = 40.76V Fe= Fe" +26; B= 4041V ‘The EMF for the cell reaction: Fe" +Zn-> Zn? + Fe a 035V Bb. 4035V 6 +117V 4d. -LI7V (IT-JEE 1989) The standard reduction potentials of Cu’* | Cu and Cu* Cu" are 0.337 V and 0.153 V respectively, The standard electrode potential of Cu” | Cu half eel is a. O184V b. 0.827V ¢, OS21V d. 0490V (UT-JEE 1997) |. The standard reduction potential values of three metallic cations, X, Y, and Z. are 0.52, -3,03, and -1.18 V respectively. The order of reducing power of the corresponding metals is b. xoYoz a. Z>x>¥ (IIT-JEE 1998) . A gas X at | atmisbubbled through a solution consning mixture of I MY-and I MZ at 25°C. Ifthe reduction potentials Z>¥ > X, then 2. Y will oxidize X and notZ bY will oxidize Zand not X &. Y will oxidize both X and Z a. Ywillreduce both XandZ ——_(UTESEE 1999) }. For the electrochemical cell, (M | M*) li (X |X), Egg) = 044 V and Ep) = 0.33. From this data, one can deduse that a M+X-—+M" + X isthe spontaneous reaction b._M?#X-—> M+ Xisthe spontaneous reaction ©. Eqgg=O.77V a. Fey =-077V (UT-JEE 2000) Saturated soltion of KNOy is ued to make‘sl-bridge because 8. velocity ofK* is greater than that of NO; by velocity of NO; is greater than that of K ¢. velocities of K* and NO} are nearly the same 4. KNO, is highly soluble in water (UIT-JEE 2001) The comect onder of equivalent conductance at infinite dilution of Lic, NaC and KCLis a. LICL> NaCl> KCL b, KCL>NaCI> Lict © NaCl>KCI>LiCl’d. LiCL>KC1> NaCl (IFJEE 2001) Standard electrode potential data are useful for understanding the suitability of an oxidant in a redox tiation, Some hal-cell reactions and ther standard potentials are given below Mn0j(aq.) + 8H" (aq.) + Se” > Mn™*(aq.) + 44,00); Paisiv Cr,0F (aq) + 14H (aq) + Ge" 9 2CP"(aq) + 7H,00); B=138V Fe™(aq.) + > Fe"(aq.) E°=0.71V Cla) +26 9 201) B=140V Identify the incorrect statement regarding the quantiative estimation of gascous Fe(NO) a. MnO; can be used in aqueous HICL . CiOF canbe wed in aqueous HCI «MnO; an be used in aqueous H,S0, 4. CO canbe used in aqueous H,S0, IT.JEE 2002) In an electrolytic el, the fw of electrons is from a cathode to anode in solution anode to cathode through extemal supply €. cathode to anode through itera supply 4. anode to cathode through intemal supply (OIT-JRE 2002) a. Y>Z>X © Z>Y>X 17, The emf of the cell Zn 1Zn°* (0.01 M)I1Fe** (0.001 M) Fe 39 YEARS] "AR CHAPTERWI p PREVIOUS YI ADVANCI JE Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi, Ph. 0861-2662628, 9696608612, 8607619968, NEWTONCLASSES.NETELECTROCHEMISTRY |JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] 298 Kis 0.2905 then the value of equilibrium constant forthe cell reaction is a, 105200501 fe. 1082500055 vb. 1992200055 a, ons (ITJEE 2004) 18, The rusting of iron takes plac a follows I +26" +%0, 9,0 0); Fe" 426° Fess); Calculate AG? forthe net process a. 3224 mot b, -161 KS mor e152 mot 4. 7645 mot (UT-JEF 2005) 19, Electrolysis of ilute aqueous NaC! solution was carted cutby passing 10 milli ampere curent. The time required to berate 0.01 mol of H, gas tthe cathode is (I Faraday 96500 C mor) a 9.65 x10" see ©. 28.95 x10" see b. 19.3 x 10" see 4. 38.6 x 10" see (IT-JEE 2008) 20, AgNOs(aq.) was added to an aqueous KCl solution ‘gradually and the conductivity of the solution was ‘measured. The plot of conductance (A) versus the volume of AgNO, is Pern 4 Volume Volume ® o b@ e® a9 (HEJEE 2011) 2 ® 21, Consider the folowing cell reaction: Wey + Oy + 4H) > 2FeR + 2HOp F= 1.67V At [Fe] = 10 M, P(O,) =0.1 atm and pH = 3, the cell. potential a 25°C is R1ATV BLIV @187V d1s7v (HT-JEE 2011) Multiple Correct Answers Type 1; For the reduction of NO; ion in an aqucous solution, E° is +0.96V, the values of ° for some metal ions are given below: Vag) +26 9 FeM(ag.) +3e° > Fe Au™(aq.) +3¢° > Au Fe=4140V He(aq.) +e" > Hg F°=40.86V ‘The pair(s) of metals that is (are) oxidized by NOs in aqueous solution isfare Vand Hg FeandAu B=-119V b. Hg and Fe a. FeandV (HT-JEE 2010) Linked Comprehension Type Passage 1: Tollen’s testis given by aldehydes. Agh +e Ag: Ey = +0800 Calt0g+H0 CyHy.0y #28426 Fe Geile o0sv [Ag (NH))J"+6° Ag+ 2NH;, £2, = 0373 2.303RT Given 8924 eso) CIT FEE 2006) 1. Calculate (a K) for Cin 0g+2AG" + 0 -» GHh,0, 42H + 2Ag 2556 96 66 5838 On ang NH, pH of the solution incresses o 11 then, iden the effect on potential of hale a. Eq increased from £2, by 0.65 1B, Egg decreased from E2, by 065V & Eegincteased from E&, by 0.65 V 4G. Eygy decreased from E2, by 0.65 V NH is used in this reaction rather than any other base Select the correct statement ot ofthe folowing a. (Ag(NH)" sm weaker oxidizing agent than Ag* by todissovetheinsoble silver oxide formed under the reaction conditions Ag precipitates gluconic acid a its silver salt 4. NH, changes the standard reduction potential of (Ag(NH,)sI" Passage 2: Chemical reaction involves interaction of sts and molecules. A large numberof toms/molecsles approx mately 6023 10° are present in afew grams of any chemi- cal compound varying with their atomicfmoleclar masses. To handle such large numbers convenient, the mole concep was 39 YEARS] 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836608812, 8507613968 NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES introduced. This concept has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry and ra Mi; Fete oF F-0n Or 4H +403 2H,0; B= 1.23 Among the following, idemiy the orrect statement, 1. Chloride ions oxidized by Op. b. Fe" is oxidized by iodine. «Iodide ion is oxidized by chore. 4. Mn" is oxidized by chlorine While Fe™ is sable, Mn is not stale in acid solution because 8, O, oxidizes Maio Mn* 'b._O; oxidizes both Mn to Mn™* ©. Fe" oxidizes H,Ot0 0, 4. Mn oxidizes H,0 10 0, >. Sodium fusion exact, obtained from aniline, on weatment with ion (Ht) sulphate and H,S0, in the presence of sir gives Prussian blue precipitate. The blue colour is due to the formation of a. FolFetCNs b. FalFe(CN)hs © FelFetCNh a. FeFe(CN eh, Passage 4: The concentration of potassium jos inside a bio- logical cell is atleast twenty times higher than the ouside. The resulting potential difference aross the cell is important in several processes such as transmission of nerve impulses and maintaining the ion balance. A simple model for such a concentration cll involving a metal M is M(s) | M (ag; 0.05, and Fe"* to Fe™* solar) IM" (ag; 1 molar) IM) For the above electrolytic cell the magnitude ofthe cel po- tential LE yl = 70 mV. (ITT-JEE 2010) 10. For the above cell A Fyi<0:AG>0 be By > 0;AG<0 © Fey <0:6G>0 dh Bey, > 0,4 <0 11. Ifthe 0.05 mola solution of M’ is eplaced by «0.0025 molar M solution then the magnitude ofthe cll potential ‘would be a 35mV b 70mV ¢. 140mV d. 700mV Passage 5: The electrochemical cell shown below isa concen- twaton cell. MMF" (strate solution of sparingly soluble sat, MX) I M* (0.001 mol dm") 1M. ‘The emf of the cell depends on he ference in concentrations B cof Mons at the two eletrades. The emt ofthe cell at 298 KZ 1s 0.059 V. (UT-JEE 2012) = 12. The value of AG (KI mol") forthe given cell is (ake IF 96500 C mol") $7 BST) Gild | & W114 13, The slbilty product (Ky ma” dv of MX 298 KF based on the information availabe the given concentration cell is (Take 2303 «x 298/F = 0.059 V) z a 1x10 b 4x10" & 1x10 3 Matching Column Type 1, An aqueous solution of X is added slowly to an aqueous Solution of Y.as shown in Column I. The variation in ‘conductivity of these reactions in Column TT. Match Column I with Cokumn Il and select the correct answers using the code given below Column [p- (CyH,),N + CH,COOH x ¥ (Column Tt Conductivity de- creases and then lg. KI@O.1M) + AgNO,(O.01M)|2. Conductivity de- x Y creases and then does not change much Conductivity in- creases and. then does not change ‘much ‘Conductivity does not change much and then inereases +. CH)COOH + KOH x y 1 1 1 2 (IEE Advanced 2013) Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi, Ph.; 0861-2662628, 9696608612, 8607619968, NEWTONCLASSES.NETELECTROCHEMISTRY |JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] 2. The standard reduction potential data at 25°C is given below (eM, Fe) = 40.77 EP (Pe, Fe) = O44 Vi. (Cul, Cu) = 40.34 V5 (Ca, Cu) = 4052 F 104g) + 4H + 4e° 9 2H,0) E°[O4g) + 2H,0 + 4e" > 40H] = 40.40; E (Cr, Cr) = 0.74; EB (CPC) =-091V Match £” of the redox pair in List withthe values given in List TT and select the correct answer using the code given below the lists (IEE Advanced 2013) st | “0.18 V 4 0.04 V =0.83V List 1 9 (Fe, Fe) gq. & 4H,0 4H + 40H) rE (Cu" + Cu 200) ss B(Cr*, Cr) Codes: Integer Answer Type 1. Allhe energy released from the reaction XY, A,G° = =193 kJ mol-' is used for oxidizing M" as M* > Mi*-+ 26", =-025V Under standard conditions, the number of moles of M* ‘oxidized when one mole of X is converted to Y is [F = 96500 C mot" (IEE Advanced 2015) >. The molar conductivity of a solution of a weak acid HX (0.01M) is 10 times smaller than the molar conductivity of solution of a weak acid HY (0.01M).1f 2°. = 2°. the Aifference in their pK, values, pk (HX) ~ pk, (HY), is (consider degree of ionization of both acids tobe << 1) GEE Advanced 2013) Fill in the Blanks Type |. Of the halide ions agent 2. Galvanization of iron denotes c is the most powerful reducing (ITE 1978) swith (HT-JEE 1983) The more the standard reduetion potential, the its ability to displace hydrogen from acids. (IIE-JEE 1986) ‘The electrical conductivity ofa solution of acetic acid will be iffa solution of sodium hydroxide is added (ITJEE 1987) . The electrolysis of molten sodium hydride liberates gas atthe (IT-JEE 1989) True / False Type 1. The dependence of electrode potential forthe electrode IM" | M with concentration under STP conditions is given by the expression login(M"™] — CIT-IEE 1993) Subjective Type 1. A current of 3.7 A is passed for 6 h between nickel electrodes in 0.5 L of a 2 M solution of Ni(NO;)>. ‘What will be the molarity ofthe solution atthe end of electrolysis? (ITJEE 1978) 2. The density of copper is 8.94 g/ml. Find out the number ‘of coulombs needed to plate an area 10m x 10m to a thickness 107 cm using CuSO, solution as electrolyte. (ITJEE 1979) Consider the cel! Za Zn°"(ag) (1.0 M) II Co™(aq) (1.0 M) Cu. ‘The standard reduction potentials are +0.350 volts for 2e + Cu"* (aq) + Cu and ~01763 volts for 2e"+ Zn"*(aq) > Zn Write down the cell reaction. . Calculate the emf ofthe cel ¢. Is the cell reaction spontaneous or not? (IPJEE 1982) In an electrolysis experiment current was passed for 5 hours through two cells connected in series. The first ell ‘contains solution of gold and the second contains copper sulphate solution 9.85 g of gold was deposited inthe fst ‘ell. Whats the wt of Cu deposited onthe eathode ofthe second cell. Also calculate the magnitudes ofthe curent in amperes. (1 faraday = 95500 coulombs) IT-JEE 1983) . How long acurent of amperes has o be passed through solution of silver nitrate to coat « metal surface of ‘80cm with 0.005 mm thick ayer? Density of silvris 10:5 Bice’ (IT-JEE 1985) ‘The EMF of a cell corresponding tothe reaction Za\s) + 2H"(aq) > Zn°*(0.1 M) + H,(g) (1 atm) 4 0.82 volts at 2 Write the halfcell reactions and calculate the pH of the solution atthe hydrogen electrode -0.76 volts: Ey, (IT-JBE 1985) Give reasons in one or two sentences: “anhydrous HClis a bad conductor of electricity but aqueous HCl is a good conductor” (IT-JEE 1985) 3. During the discharge ofa lead storage battery, the density of sulphuric acid eel from 1.2940 1.139 liters of the acid and the volume remained practically constant during the discharge. Eastizy Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 8507613968, NEWTONCLASSES.NET ) PREVIOUS YEAR CH ADVANCI JER. K. MALIK’S NEWTON CLASSES Calculate the number of ampere-hours for which the ‘artery must have been used. The charging and discharging reactions are: (UIE-JEE 1986) Anode: Pb + SOP Cathode: PbO, + 4H'SOF + 2e"= PASO, + 2H,0 (discharging) Note: Both the reactions take palace atthe anode and cathode respectively during discharge. Both reactions get reverse during charging 1. A100 watt, 110 volt incandescent lamp is connected in series with an electrolysis cell containing cadmium sulphate solution, What weight of eadmium will be deposited by the curren owing or 10 hours? (IT-JEE 1987) A cell contains two hydrogen electrodes. The negative clectrodeis in contact with a solution of 10-°M hydrogen ions. The EMF of the ellis 0.118 V at 25°C. Caeulte the concentration of hydrogen ions atthe positive electrode. (ITJEE 1988) Ina fuel cell hydrogen and oxygen react to produce electricity. In the process hydrogen gas is oxidized at the anode and oxygen at the cathode. If 67.2 iter of H at STP reactin 15 minutes, whats the average curent produced? ithe entire currents used for eleeto deposition 0 copper from copper(I} solution, hw many grams of copper will be deposited? CIT-JEE 1988) 2. An acidic solution of Cu” salt containing 0.4 g of Cu™™ is electolysed until all the copper is deposited. The eleetolysis is continued for seven more minutes withthe volume of solution kept at 100 ml and the eurent at 1.2 ‘mp, Calelate the volume of gases evolved at NTP during the entre electrolysis (IT-JEE 1989) ‘The standard reduction potential at 25°C of the reaction 2H,0 + 2¢ <= H, + 20H is -08277 V. Caleulat the ‘equilibsium constant forthe reaction (ITT-JEE 1989) 2H,0 = H,0" + OH at 25°C ‘The standard reduction potential of Cu"/Cu and Ag'/Ag electrodes ae 0.337 and 0799 vol, respectively. Construct a galvanic cel using these electrodes so that its standard e.mf. is positive. Or what concentration of Ag* will the ems. ofthe cell, at 25°C, be ero if the concentration of Cut" is 001M? CUTIE 1990) Calculate the quantity of electricity that would be required to reduce [2.3 g of nitrobenzene to aniline, ifthe curent efficiency for the process is $08 ifthe potential drop across the cell is 3.0 volts, how much energy will be (IT-JEE 1990) Zine granules are added in excess to a $00 ml of 1.0 M nickel nitrate solution at 25° C until the equilibriums reached. If the standard reduction potential of Zn’ | Zn and Ni?" | Ni are ~0.75 V and ~0.24 V respectively, find ‘out the concentration of Ni? in solution at equilibrium. (IEJEE 1991) PHSO, + 2c" (charging) consumed? 17. Acurrent of 1.70 is passed through 300.0 ml of 0.160 M solution of ZnSO, for 230 sec. with acurrent efficiency of 90% Find out the molarity of Za after the deposition of. Zn, Assume the volume ofthe solution to remain constant during the electrolysis. (IT-JEE 1991) . For the galvanic call: AglAgCl,y, KCI(O.2 M) Il KBr (0.001 M), AgBrgy| Ag Caleulate the EMF generated and assign correct polarity teach electrode for spontaneous process after taking into ‘account the cell reaction at 25°C, IK (AgCl) =2.8 x 10, K(AgBH) =3.3 x 10) (UE-JEE 1992) ‘An aqueous solution of NaCl on electrolysis gives H,(@), Cli) and NaOH according tothe reaction: 2CK- (aq) + 2H,0 = 20H (aq) + Haig) + Ch. A direct current of 25 amperes with a curent efficiency ‘0f 62% is passed through 20 litres of NaCl solution (20% by weight). Write down the reactions taking place at the anode and cathode. How long will it take to produce 1 kg cof C1,2 What be the molarity of the solution with respect to hydroxide ion? (assume no loss due to evaporation.) (IT-JEE 1992) “The standard reduction potential forthe half-cell NO} ug) + 2H ag) + € > NOC) + H,0 is 0.78 V. ‘a, Calculate the reduction potential in 8 MH. . What will be the reduction potential of the half-cell ina neutral solution? Assume all the other species to be at unit concentrat (IT-JEE 1993) (Chromium metal can be plated out from an acidic solution Containing C10, according tothe following equation. C10 gy + OH ug) + 667 9 Chg) + 3HQO Calculate () how many grams of chromium will be plated ‘out by 24000 coulombs and (i) how long wil it take to plate out 1.5 g of chromium by using 12.5 amp current? (HT-JEE 1993) 3. The standard reduction potential ofthe Ag*/Ag electrode at 298 K is 0.799 V. Given that for Agl, Ky, = 8.7 x 10", evaluate the potential of the Ag'/Ag electrode in 4 saturated solution of Agl. Also calculate the standard reduction potential of the T/AgV/Ag electrode. (ITE 1994) The Edison storage cells is represented as Fe(s) | FeO(s) | KOH(@q) | NOY) Nis) ‘The half-cell reactions are: NiO) +H,0() + 26° —*2Ni06) +2017 E"=+40.40V Fe0(s) + H,0() + 26° = Fe(s) +2 OF; E* =-0.87V fa. What isthe coll reaction? 'b, What is the cell em? How does it depend on the concentration of KOH? :- What is maximum amount of electrical energy that ‘ean be obtained from one mol of Ni,O,? (IT-JEE 1994) ST 39 YEARS} D PAPERS IL ) PREVIOUS YEAR CH ADVANCI JE Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi, Ph.; 0861-2662628, 9696608612, 8607619968, NEWTONCLASSES.NETELECTROCHEMISTRY |JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] Although aluminum is above hydrogen in the lectrochemical series. itis table in air and water. Explain IT-JEE 1994) An excess of liquid mercury is added to an acidified solution of 1.0 x 10 M Fe™. Iti found that 5 of Fe" remains at equilibrium at 25°C. Calculate Ejg.2¢| yp assuming that the only reaction that occurs is 2 Hg + 2Fe — Hel! + 2Fe"* Given: (B° pdeyyct+= 0.77 V) (IT-IEE 1995) ‘The standard reduction potential for Cu"* | Cuis 4034. Calculate the reduction potential al pH = 14 fr the above couple. K,, of CHF), is 10x 10 CITJEE 1996) 7. Electrolysis fa solution of MnSO, in aqueous sulphurie acid is a method for the preparation of MnO) according to the reaction: Ma?* (aq) +2Hj0 MnO,(s) +2 H" (ag) +Hy(g) Passing a current of 27 A for hours gives only 1 kg of MinO,, What isthe value of curent efficiency? Write the reactions taking place at the eathode and atthe anode (ITE 1997) . How many grams of silver could be plated outon silver in +1 oxidation state for period of 0.8 hours ata current of. 8.46 amperes? Whatis the area ofthe tray ifthe thickness ‘ofthe silver plating is 0.000254 cm? density of silver is. 1055 gfem’ (UEJEE 1997) . Calculate the equilibrium constant forthe reaction Fe" + Ce Fe + Ce* (Given: Eeqineade)= 144 Vi Byte = 068 V) (UTE 1997) CCleulate the equilibrium constant forthe reaction 2Fe* + 3 = 2Fe* + 15. The standard reduetion potentials in acidic conditions is 0.77 V and 0.54 V respetively, for Fe Ie and Ij” couples. (IT-IEE 1998) Find the solubility product of a saturated solution of AgsC1O, in water at 298 K ifthe emf ofthe cell AgiAg* (aid. AgjC+O, soln) Ag? (0-1M)Agis0.164V at 298K. (IT-IJEE 1998) Acell, AgiAg* 1Cu?* ICu, initially contains 1 M Ag" and 1M Cu? ions. Calculate the change inthe cell potential ater the passage of 9.55 A of current fo Ih (UTE 1999) Copper sulphate solution (250 mL.) was electolysed using platinum anode and a copper cathode. A constant curent of 2A was passed for 16 minutes It was found that after electrolysis the absorbance ofthe solution was reduced to $0% of its original value. Calculate the concentration of copper sulphate inthe solution to bepin with (UIT-JEE 2000) J. The following electrochemical call has been setup. Pu) Fe, Fe (a= 1) 1Ce*, Ce (a= 1) 1PL2) Ee, Pe) 20.77 V; E(Ce*2Ce) = 1.61V If an ammeter is connected between two platinum clectrodes predict the diection ofthe flow of curen. Will the curent increase or decreases with ime? (IEJEE 2000) 5. The standard potential ofthe following cell is 0.223 V at 18°C and 0.21 V at 35°C: PUI HG) |HCI(ag)|AgCIGS) Ags) Write the cell reaction Bh Calculate AH® and AS* for the cell reaction by assuming that these quantities remain unchanged in the rang 15°C to 35°C. «Calculate the solubility of AgCI in water at 25°C. Given: The standard reduction potential ofthe Ag"(aq) | AgG) coupe is 0.80 V at 25°C (ITJEE 2001) . Two students use same stock solution of ZaSO, and a solution of CuSO,. The emf of one cel is 0.03 V higher than the other. The cone. of CuSO, in the cell with higher emf value is 0.$ M. Find out the cone. Of CuSO, inthe ter cell 2.303 RTIF = 0.06.) (IE-JEE 2003) Fn the equilibrium constant forthe reaction, Iu?" Cul" In Cu" at 298 K 040 (IT-JEE 2004) 15 Vs Efe tet 38, a. Forte reaction AgS(aq) +C1°(aq) > AgCl(s) Given: ~|-26; darinon Ag" (aa) +71 cr (aa) =19) AgCls) =109) Write the cell representation of above reaction and calculate Ely at 298 K. ‘Also find the solubility product of A&C. If 6.539 x 10 g of metalic zinc is added to 100 ml stated solution of AgCL. Find the value of zs (as'T How many moles of Ag will be precipitated inthe above reaction. Given that Ag+e Ag E=080¥ Zn 426-970; F =-0.76V (UT JEE 2004) 39. We have taken a saturated solution of AgB, whose Kis 12x 10° If 10" M of AgNO, are added to 1 L of this solution, find the conductivity (Specific conductance) of the solution in tems of 10° Sm units Given Ring =6% 10° S ne mol! 8x10? Sm mol Species VOR. ‘ey (UT-JEE 2006) Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 8507613968, NEWTONCLASSES.NET ST 39 YEARS} D PAPERS [L ) PREVIOUS YEAR CH ADVANCI JEUsa a UE aga SUES Ea a ya a ae RE a #RKMALIKSNEWTONCLASSESELECTROCHEMISTRY [JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] Hints and Solutions Mt Ua SSRN @RKMALIKSNEWTONCLASSES JEE ADVANCED Single Correct Answers Type gm A _ ‘eletion poental valve 2 isthe strongest reucing agent among the given options. ‘The substance having smaller valve ofthe reduction potential ae beter ducing spent WB Zit WB Zit Here and E, ae equivalent weights ofthe ions, ‘Te eduction potential (a ive) ofthe ions ar inthe onder: ‘Ag’ > Hel! > C2 > Mg Mgt (a) ill not be reduced as its reduction potential is such lower than that of water-083 V). ence the sequence of deposition of the metals willbe Ag, Ha, cu Ja Reducing powers Cars of one mol of letras = 96500 Tam eqialent of aubeanc wl be deposited by one mole f elton 12H, () + AgCI(®) HT (ap + CT (a) AR) ‘There is oxidation of drogen and recto ver, there fort cers in the lowing cl PLL (@) IHC Goi) Ag) AR ‘When ead soe ater is dncharge, subi aci icon sine Water is reduced at te cathode and oxi the anode instead of Na* and SOF (Cathode: 29,0 +26" H+ 205 Anat: 140-421" + 10,42. 8. Ina galvanic col oidatn oscr at anode and reduson occur et exo. fi Oxidation ours at electrode having higher oxidation potential and it behaves as anode and ther electrode acts bs cathode. Mh Ba=Ec-E, (Gabsiute reduction potential at both places) Fe" 4 Zn Za" + Fe ‘Zn->Zn"* +26" and Fe™ + 26° Fe ‘Znis anode tnd Fe is cathode. Hilfe reaction cuicy C42 =O etic Ose =u orice otte=ee From the haf-cell reactions, it follows that 8G} = AG} AG? 20.337 V) 0.153 =0.521V ‘More negative o lower i the reduction potenti, more i the reduing propery. Thus the reducing power ofthe corespond- 7, ing meta wll follow the reverse order, ie. ¥ >Z>X. a. The smaller the reduction potential ofa substance, the more is its reducing power and less sits oxidizing power. ‘The given order of reduction potential is Z> Y>X, The order of oxidizing power is Z> Y > X. ‘Therefore, ¥ will oxidize X and notZ 9. That reaction is spontaneons where cathode i of higher reduc ‘ion potenti 8 For M's X09 M4X, Bug =044=0.33=0.1 Vis postive, tence easton i spntanes ‘The salt used to make ‘salt-bridge” olin ti tic rmobiliy of ction and anion ar of comparable order so dat they can keep the anode and cathe hal ells weal tall times KNO, is wed because velctis of K* and NOS fon are ary Same 2 AS we go down the group 1 (i. from Li* wo K"), the onic = radius increases, degree of solvation decreates and henee effecive size decreas esting in increase in le mobility. “Hence, equivalent conductance at infinite dilation increases in = the same onder. 15. a, MoO; will oxidize CI ion according to equation Man'* + Se Nen* 2 Ch, +28 Ths, Fay = Bagg + ES scr 131-140 0.11 V oF reaction is feasible. Ma; wil oxidise Fe tae" Mn’* + Se» Mn* FoR +e Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 8507613968, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES “Tha, Mat; wl ovdse Feo Fe™ in agpoes HC medio swells also onne CT to Ce Seb onsen shold ‘not oxidise CT to Cl; and should only oxidise Fe" to Fe™ in ton trons. 16.6. Inn lect cel, cuet flow fom and o cathode and thus elestons berated a anode flows fom anode o cathode 172m Zal Za (a= 0.1 M) UF (2=001 M) IF, he el ection A. Zn(s) -> Zn™*(aq) + 2 Ah. Fe (aq) + 22" Fe(s) ‘Zals) + Fe*"(aq) 9 Zn" + Fes) ‘onapplyng Nemst equation, — 0.0591 | kzn**) ” bl al o1. ‘aor 0.2905 = Fy —0.02905 x log 10 02905= 2, ~002505%1 2. y=0.2905 +00295 =032V Ateauibiam Ean = 0) (reduction potential are compared) WAG =-nFE Fels) 9 Fe #26 2H? + 26" +0, 040; Pets) +210 +40, FP + H0: Ely =123-(-044)= 1.67 AG =-nF Ey 19.) Given E=044v Ba4123V treo Beco 1F produces 05 mole (0.01 mole is produced by 38. AgNO,(oq) ~ KCi(aq) + AgCI(s) + KNO,(0a) Conductivity of te solution is almost compensated de 1 for- satoe of KNO¥ag}) However, after at end point, conductiy- ity increases moe rpiciy due to ain of excess AgNO, solution. whic ead to large number of ins. 21.4. 2Fe(s)+ Og) + 4H (ag) > 2Fe"iag) + 24,00) {N =4 (a0. of moles ofeleroninvelved) From Nemst's equation. o Fa= Ee 08 0 ost, 40 aot 4 Fo1xa07 #167-0106=157 6 a) =10*) Multiple Correct Answers Type 1 ag bade ‘The species having less reduction potential with respect 0 NOSE are V. Fe and Hg Linked Comprehension Type 1.4. Inthe given reaction, Ag* ions are reduce to Ag and glucose is ‘oxidized ogluconic acid as per the given reactions, Ag+ Ag: Bly =+ 08000 C4lh,,0,+¥0-+ Calh0> +24 +26 Eig =-005 Ver 8, =0.08V 8-005=075V “RT In K Gig =-nFE=-2F x07 2F = wx 2E 075-2 38920755838 Ke FE 075) =2 3892 ‘On increasing the concentration of NF, the concentration of HT ions decreases, therefore x210g10"" [=pH att 9[H"1=10"M) 0.089211 =0.65V Ths, Eis increased by a factor of 0.65 from E, During Tollen’s test, oxidation of silver ion requires an wk + 0.96 V) willbe oxidized by NO} . These species ) PREVIOUS YEAR CH line medium. Under these conditions it forms insoluble silver & ‘oxide, hence to dissolve this oxide a complexing agent, armmo- nia is added, which brings silver ion as diamminosilve (2) fon, TAg(NH,).1 tis a soluble complex. Reaction at anode :2CI'—+ Cl, +26" 1 L solution of NaCT has 4 moles (0.5L solution of NaCI has 2 moles = 2moles of CT gives I mole of Cl 1. 500 ml of 4.0 molar NaCl has 2 mole of NaCl By elearolyis wo can get a maximum of 2 moles of sodium Which can combine with exactly 2 moles of mercury to give smalgam, ‘The maximum weight of amalgam which can be formed. from this solution = weight of mole of sodium + weight of mole of mereury =2« 23 + 2x 200 = 446 g Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi, Ph.; 0861-2662628, 9696608612, 8607619968, NEWTONCLASSES.NET ADVANC JEELECTROCHEMISTRY |JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] 6d. Nav +e Na ‘Total numberof moles of Na* discharged a cathode = 2 mole ‘The numberof electron requied for this purpose =2 mole ‘Same no of eleetrons wore required for liberation of Cl ‘Total charge required = 2 faralay = 2 96500 = 193000 coulomb. Concept: EIM.F. Es calculated sing ‘= Reaction for which is postive i spontancous cr+0, 40" +c), =-0.13 = negative = non-spontancous yt Ret re 420 0.14, negative, so non-spontancous Ma?" +0, Ma” +10 B=123- 150 ~0.27 = negative = non-spontaneous =-0.46 = negative => non-spontancous AMIN" + 21,0 4Mn* +0, +48 Exyxmige + Eigo, =150+ 123027 So, (@ is reverse of (a 30 spontaneous NatC+N— , Necn Fe" + 60" FeACNI APO + 3IFICN)I —> FelFe(CNIgh, 10.B. Miy* Mins > Mages Mi Accor sing t Nernst equation, 30BKT | Mis ona aa is O28 electrodes ae of same materia 2303R7, 3 T logs x10 Fee = Eg =0.70'V and NG < 0 fo the feasibility of 11.€. From above equation = 2X" (ag) + MXsfag) + 26 Atcathode: M™ (aq) + 22° Mis) factor ofthe cell restion i 2. 11a Mimole 13,0, MIM Cag) (ag) IM ani M Mi, = at given cone Mi, => saturated solution As electrode is same so a0 Anode: M—> MM(aq) +26 Cathode: (aq) +26 —> M M* (aq), == M** (aq) 2 fas, } 10° (As elected is sae 0 Egg = 0) M’* = 10°= solubility ofa satin saturated solution, 2 Kah a4 x04 x10 Matching Column Type La (CoH) CH,COOH ~» (CH),NH + CH,COO™ x ic Initally conductivity creates det ion formation after thatbecomes pty constant becaieX alone canot form ions. Hence (3) is the correct match. Lo - _KI(0.1M) + AgNO,(0.01M) > Agi) + KNO, x y amber of fons i he solution remsns constant un al the AgNO, prespitted as Agl. Thereafter condcance jincreases due to increases in number of ions. Hence (4) is = the coneet math : e Tily conductance decreases de tothe decrease in the Z number of OH” ions thereafter it slowly increases due to = the increase in arte of Hons. Hence (2) th comet math, < Intl it decreases do to detest in fons and then {increases due to the increase in OH” ions. Hence (1) is the > comet ath + AG Pnge= BOR ps + AG AB PE gag =—1 FE gg HDX FES ge) Fh =H0OKV Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 8507613968, NEWTONCLASSES.NETR. K. MALIK'S NEWTON CLASSES 4 Oy(g)+2H,0+4¢"408" =040V 2H,0-30,(g)+4H"+4e" Be =123V So, 4H,0—==sH" +408" F for II" reduetion = 0.40 - 1.23=-0.83V MOR s0y AGS joven Gene) * 46 AB FEB gy =D Faye HOD FE Integer Answer Type L@ Xo Mio Mt 426° Hence AG* for oxidation will be A =-nFE 2x 96500 x (025) = 48250 1= 48.25 KI 48.25 K] energy oxidises one mole M* 193 193 k energy oidises 73 # + male M*=4 mole MT 2.) 1oHK car Bn Fill in the Blanks Type 1. T-(+ Inis weakest oxidizing agen) Oxidizng power: F,>Ch > Be,> Ie Reducing power: F- Zn” +26 Reduetion half reaction: Cu" +25" Cu Thus the cell reaction wil be: Zn + Cu"? + Za? + Co HL EMP of cell, £2. = ESute~ Esa = E2, cy~ Ey an Ely =0.350—(-0.763) 0.360 +0.763 volts = 1.113 vols IW. Since emf of the cells positive, dhe reaction as writen is spontancous. Gold deposited in the first cell = 9.85 g At wt of gold = 197, oxidation numberof gold = ) PREVIOUS YEAR CH ANC (vere m stands forthe weigh of ions deposited, for carent,&, 1 for time and 2 for electrochemical equivalent ofthe electro. = Tye) JE ye 1396500 197x3x 60x60 250525 _ogos2.a Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi, Ph.; 0861-2662628, 9696608612, 8607619968, NEWTONCLASSES.NETELECTROCHEMISTRY |JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] 13 According to Faraday's second law, Weof Co Eq.weof Ca 985%3, 635 _ > Woof Cu deposited = Jepsen = 285% 4.7625 2 Sen x00 en 650 emt SOS xO em 500 ste 6, Haran gaco ie Ei +2 Zn tee Ler sarin Weiner a oe BOAT mE Eg Ea 0.059), 1 0716-29910 5, 076 — tog g, 076-0059 met Sint) Egg Fg, "Ein ah Fen ey 200) - og oP Foy, (0089 opt"), 0.059 —log H"1=-0059% pH Now since B =F, Flonmn E =-0.059 pt ~ (09) 0.28=~0.089plt+0.79 pH 1. Anhydrous HCl is non polarcovalent compound. Hence, itis ‘had conductor. On the other hand, an aqueous solution of HCL has H® and CT ions. Hence itis @ good conductor, Iinlead storage battery the anodic and cathodic reactions during discharge (ot operation oe working) ae a: 1. Anodic reaetion: PWS) + SO jy) > PESO yy + 267 4 Cathodic reaction: PRO) + SOliay + 4H, +267 + PDSO yy) + 20, Inboth the halfcel reactions H,SO, is consumed ad hence ‘one, of H,S0, decreases during the working (discharging ‘ofthe battery. For the withdraw of 2F = 2 x 96500 C of clectic charg, 2 mol of H,SO, ae consumed, Density of H,$0 solution (sed as lecuoye falls uring working of thecal Both esctions gt revere on charging the batery leading to regeneration of H,S0, Former anode but no eatbode ecbargng) 050, +26°-> Phy + SO%xy Formed cathode but pow anode: P6045 +209» PHOay + SOR + AHay 4 26> Carat ae Watt = Volt 100= 110 Current _100_10 * hon Now we know that 0. 1 minim Pxr0xr600% 0339x1124 2 =0.309F W+ of cadmium deposited = For a concentration cell 0.059, 9 yo, Fa be 9.06 g I is a concentration cell as both the electrodes are made of same element. Negative electrode acs as anode in a galvanic cel, Atanode;Hy>2H+2° H'] Atcathode; 20°+ 26" Hy [H]= = GG Anode reaction: H; + 20H” 9 21,0 + 22° Cater 10,140 26 2000 For the given reactions its obvious that 224 ines of H, gas require 2 Faraday electcity. 2672 lites of H will prodce = 6 Faraday electricity qelt 6% 96500 = 1% 1560 96500 S965 643.3 ampere Sine Pap= 8 poten SF ign 8176 , rim atta uma Bont yo At cathode: Cu +2e" > Cu 4x2 @6 2.58% 10° Equivalent of O formed = equivalent of Cu Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 8507613968, NEWTONCLASSES.NET 39 YEARS] ) PREVIOUS YEAR CH ADVANCI JER. K. MALIK’S NEWTON CLASSES For second par of electrolysis: Since Cu" ions are discharged completely and thus futher passage of current through solution will lead to following changes: ‘At anode: 2H,0 4H +0, +4e~ Ar cathode: 2H,0 + 22" H,+ 20H ‘Thus, equivalent of Hy = equivalent of O; _Ut__12%7%60 536500” 96500 _ Total equivalent of O, = Equivalent of Op for fist part + Equivalent of O; for second part of electrolysis 5.22% 10 + 1258 x 107 =17.8x 107 “4 equivalents of O, at STP =22.4L 178 x 10° equivalent of O, at STP 52x10 _24x178x10" 4 Now. equivalent of H= 5.22 x10 2 equivalent of H at STP BASE _sasot “Total volume of H, at STP 99,68 mL. _AXS22%107 66 6a. “otal volume of 0, + H, = 99.68 + $8.46 = 158.14 mL. Consider an electrode of hydrogen (H,) 88 2H +26" Hy: Given electode is 2H,0 +26" 9H, + 208 Eoag £000 > Fey for Hy ‘Therefore cell reactions are: ‘Anode reaction H+ 208 28,0426; Cathode reaction: 2H +26" 9 Hs [Netreaction: 2H" + 20H —*2H,0 = or oT (OnF For the reaction, 24,0 [1,0"] 1041) 07] (OH Thus, K: Also, Ea * Eoat ,0)* Exton 0.059 (HOF Fo) 8 ORT 05) et 2082774 299 og (our eH OF pee oH oe TOF xia 1 =09277 +9? tos From Eqs. (i) and (i), 082774 9S bk, if Baa Acowulitrom, Ey =0 “08277 =0.059 los Ky agar 0039 14 Concept: In working galvanic cltahode is always of higher redcton potential Foyt 037M Ea Fagg Fbongs 2099-0337 = cus2ag' Cu Ag: Fay Hence he alvanie cell in question wil consist of anode of copper and cathode af sive. Calelation of concentration: or los, or k= 9.35 x10" [Products] Reactant] =p 2.059 jog (CHP IAS “ths mn * (CuliAg’ Fuga £2: [n=2] 1S, CyHANO, + 6H" + 6¢"—> CHJNH, + 2H,0 M, wt of HNO; = 72 + 5:4 14 +32= 123 Reduction of 123g of nitrobenzene requires 6 F of electricity 1s 6 moles of electrons ae required. Reduction of 12.3 g of nitrobenzene required oF = E123 g06F tag = 06 x96500C= 579006 Since current efficiency is only $0% (Quantity of current required for reduction 39 YEARS] ) PREVIOUS YEAR CH ADVANCI JE Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi, Ph.; 0861-2662628, 9696608612, 8607619968, NEWTONCLASSES.NETELECTROCHEMISTRY |JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] 13 16, The reaction tobe considered is, Za\s) + NP*(aq) = 25"(aq) + NUS) ‘The cell involving this reaction would be ‘Za(s)| Zag) WN" (aq)INi(9) Faq -0.24-(-0.75)=051V nFE*___nE” _2x051 2.303 RF “0.0591 0.0591 Kgl. 782e108 Let x be the concentration of Ni* that have been reduced 10 nickel at equilibrium, ‘afs)+ Ni (aq) —* Za aq) + Nils) (aa) <"NM] O-3) x=10M log So, 1.7810 a0 So GIN T8507 nit =1.30%230=391¢ Amount of change actualy used 0 PO 3012351 9C 100 2a + 26° En 2 F products 65 g of Zn 351.9C gives X351.90f Za 796500 228735 BIST 4 0.1185 gf Za 193000 ® i oanss: 0.00182 "an Gs “Molarity of Zn after the deposition of Za ( 1000 10M -| 1100) aan wont -(oooisas x2) mwo.sim ‘ABIAGCIs), KCl (0.2M) 1 KBr (0.001M), AgBUG) | Ag ‘Anode Cathode Kg(AgC)=28% 10" Ky(AgB=3.3% 10" At anode, AE—> Ag! +e Atcathode, Ag" + 2° 2A8 + Cell reaction :AB-+ Ag" = 2Ae-+ Ag” ‘The subscripts 1 and 2 on Ag denote the species concerned ‘with anode and cathode respectively Applying Nemst equation 0059 ., [Ee] Reactant GyAg]=bAe]=1 Ky (AgC) =28% 10" or 28x10" 02 these are in solid state) Ag‘) IC] = 2.8 10° =14x10" 2) Ky (AgB®) =33 10° oF nae tne 22228 1 fase] [eAg*] [Be] =33 x 10°? 3x10 T 33x10" atm) Since emis nega taneous. For the reaction tobe spontaneous, its emf shouldbe positive i.e, B= 01037 V and its polarities should be reversed ie. anode should be made cathode and vice-versa, So the galvanic cel ‘Ag | AgBr(s), KBrll ARC), KCL Ag In other words, Ag ‘AgBr acts as anode and AgCl Ag acts as exhode 2CF (aq) +2H,0=204F (aq) + Hyg) + Cle) Reaction a anode: 2CT' + Cl, + 26 Reaction a cathode: 2H,0 + 26°» H, +2087 in x2 100 ‘Weight of Cl, deposited = 1kg or 1000 ¢ We know thar Ha 2. EFF 1000 _154xt 355 96800 = 175300 see oF 48.69 hours 0.059 «0.6276 =-0.037V this shows thatthe rection is non-spon- Samperes No.of moles of Ci; ths produced ‘Amount of OH released inthe electrolysis >. For the halfcell reaction [NO;(ag)+2-(aq) + ¢°-> NO, (g)+H,0.0) ‘The Nemst equation is E = £° 2.259 og (Product) mF [Reaetants] ‘Substituting the values in case @) 78 ~ (0.059) x(14)=~0.046 V (C10, + 6H + 66° Cr+ 31,0 1. To deposit 52g of Cr, 6 Fis required 696500 C deposit 52g of Cr 52 24000 = 2.1554 g of Cr. 125 ampere, s2xI25xt 6% 96500 1336.15 see Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 8507613968, NEWTONCLASSES.NET ) PREVIOUS YEAR CH ADVANCI JE16 R. K. MALIK’S NEWTON CLASSES 2. 4, £° = Standard reduction poteml of the Ap"/Ag electrode = 0799 gl) — Ag+ Ky=fAg}(T1=87 107" (gives) 11°" the solubility of Agh then Ky 5= [hy = {87107 =9327x10% mot (ag']= (7) =9327x107M Reaction: Ag’ +e"—> Ag 0.059, 1 £9 O50 nia) Ee a 1 9327x109 c+ Acivity ofthe electrode mater in pre Sli stat is taken as one] 0799 0059 og 0.107210" =0.799-0.474=0325 V ‘sesin LHS electrode reaction: RHS. electro action: AgIG)—> AB +T Call reaction Age) > Ag+ Equiiteum constant = (Ag*](F]= 8. 10" ‘The standard cll emt E° andthe euiibiom constant k are tated by te expression. Fay = hog K 0 298K Ag Ag te 7x10" = 01059 log 87% 10°" = 0.059 [09395 17] = But Boe = Exns.~ Fius. Egus = Feat Ely = 094840799 = 0.149 V L. Given E%,0,e00= +040 Vs Efaoge = —0387 V As reduction potential of NiO; is more than FeO, Redox changes canbe writen as At anode: Fes) + 20H” > Fe0(s) + H,O() + 26" ‘At cathode: Ni,O,(8)+ H,O() + 26 —9 2NIO() + 208 Cell reaction: Fe(s)+ Ni:Ox(s) — FeO(9)+2Ni0G) Eea= Ei.0,040~ Fre =087 +0.40= 127 Its independent of cone. of KOH Electrical energy = nFE qa = 2965003" x 127 245% 10° ‘The thin protective layer of oxides of aluminium is formed which prtees the metal from further attack of water and air and make it stable 2g) + Inia cone Equib. cone ae Het +e 10x10? 0 o 0.08 x 10° wae 095x107 0059 Fe Files") TE Avequilibrium, = 0 02077 ~ Fhe (0.95%107)%0475%10) (0.05% 1077 (On usual eaeulations, Ek ny [At pH = 14 (H°] = 110M; (087) = 10° (1) (OT =1 10") ‘Cu (OM ioises as follows: Cu(OH), = Co" + 208F K., of Ca (OH), = [Cu] (OH? ic 0F [ev"]=1.0% 10M “The standard reduction potnil of Cu"VCu is represented in the form of following equation Cu, +26" Coys (On applying Nernst equation -072v 96500 256 Current efficiency = 755100 = 94.8% Wa Reactions taking place a electrodes are AAtanode : Mn"? > M+ 26" A ethode : 27+ 2¢"-> Hy . m=ZIt gage 36500 gw Ett 10886 86060 = 96500, 96500 a v Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi, Ph.; 0861-2662628, 9696608612, 8607619968, NEWTONCLASSES.NET 39 YEARS] ) PREVIOUS YEAR CH ADVANCI JEELECTROCHEMISTRY |JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] Fey Petre ie*=08ev Col +e" eye =Lasv tae ape 4-068=40760 076 ‘0591 For the change Fe + AT eb aFe* + 1, 0.059, 059 B28 ogk, oF ioak, or B= OS (> at equilibrium, or logo K,= 12859 +.K,=76x10" oak, Alo Ela Fin =077-05¢=0239 y= Fag ag, Ey Aci, ag rai oar= Sige, |. Te cal atone rin Ag1Aa" ARCO, SY AE IND] As B= 0164 Ateathode: Adaya 7-9 AB (Using Nemst equation) Atmode: Ag Aft [Natreecton : ABSanie? Ati: B= 0164 ‘Thus bere, n= 1, B= 0.164 V,[A6"Tan =0.1 M Let the sliity of Ag,CrO, be SM Since Ag,C1O, gives? Aa" Here concentration of (Agnus =25M 1059 IA" 1 TAR adie 0.059, 25 20g: For AgiC1O,; Ag,C1O, == 2A4 + COP Kn QS a4? ce Kya (08485 104 = 244 10" Fora cell Ag! Ag’ ilCu"1Ca Cell reaction i 1 gm sepa Aa( + LO" (aq) —> asd + LUG) (n= As we know that mazatete OY x ret 6500 seat or gram equivalent of Cu" xIxt a 96500 sho x9.65%60%60=0.36 96500 Decent in the concentration of copper fon is 92° Bw maining sonentaon of oper = I~ 0.18 = 082M. 0, Increase in the conentation oar ions 0.36 M Now concent of sitet ion= 1+ 036-1364 On applying Nene exuaton 2, 20591 jg {ABD nO feu] 0.0591 5 (Ae) TO Change in ell potential, 0.0591, 1.36 20991 jog 136. = oo10v 1 * Jos m= = x2 x10" 16% 60 2596500 (65:5%16 60.10 96500 We of Cua 505 elecrolysis of CuSO, 685316.60,10" 96500 We of Cat 100% electrolysis of CSO, 815216 460.10 — 96500 C280, = Ca =0.198 10" mo 1000 19810 x Oe 19863510" + Cone. of C80, =795% 10° mol. Given, Feyejcye = LOL VEE pg 0.77 ‘Thos for Ely to be postive following reaction should occur Col + Fo Fe + Ce! Hence Ce“/Ce™ electrode will act as cathode and Fe"VFe clectrode will act as anode. ‘Therefore current will ow from Ce electrode to ron eleotode ‘Curent wll decrease with ime, . Le The half cell resetions are mse Eno Atcathode ABC y +6" ARy)+ Cli Toca acon i, + ARC Hy Atay ae ‘We know that AS = Hi. Wenow that aS= nr n> No, of transfered electon Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 8507613968, NEWTONCLASSES.NET 39 YEARS] ) PREVIOUS YEAR CH ADVANCI JER. K. MALIK’S NEWTON CLASSES P+ Faraday number = 96500 covlombs 4 — Ditference of elecure potential at two different ° AEF 30123 x 96500 J =-22195 J mole 22195 ~288 (-96.5) 9987 Hole « om = -#xar-(o-22 x0) The coresdng el ipa a AB ABC ABCly MAB) tne ef xe ect pen ia Erte ~ Ease = Eran Enyageucr nas (2 058¥ Eo 2 oa Kg AgCly As" + Cr Fe ig tae Her ig 0.0591, Therefore 0.58 = 9a ky of log Kg=-98139 101861 Kn 15410" Key of AgCl= 1.54% 10° (mole Lite"? Solubility of AgCL [eq = isti0"* = 1.24% 10° mole. 36, Daniel ellis Za!'20™ 1 Cu" 1Cu Lat there be to Daniel cells wit thei Ey a8 given Below Zai Ze) NCA ( Za\Za"(c3)1Cu2*(C=05 M)1Ca where E> E According to question, EE, = 0.03 and C, ‘The cell reactions tea} Zane ca*-520% +60,0= 281 oa) 06.05.05 0.03 = 2% jog 25 > og 9S 2 tg he or C=005M "The required reaction can be obtained in the following way. Cut +e cut +e iat Int 4267 a alding, C+ In la + Gu, B =-059F Now we know tht =n F°=~059 F o 059V or iy =059V Fey 2 hop be writen as: Atanode: —Ag(s) + CT (aq) —>AgClis)+° Atanode: —Ag*(aq)-+¢"-¥ Ag(9) Complete reaction Ag”) + CT (aq) —> AgCI(s) Hence cell representation is ‘Ag(s)AgCNs) ICI Ag™ aq) LAGS) AG" = AF (AgCD ~ Lag? (AB + ag? (CD) 109 ~ (129 +77) = -$7 kfm! = $7000 Jmol We know tha, AG? = ~nF Ey 7000 = 1 96500 % 2 (on lectro tanserred 57000 3009 059 vos O59 on x, ja 25g ARC Sag Cr) 0.0591 (1 RB Ea Ea cr lop Ky==l0-9 Ky When Zn is added 100 mio saturated AgC1 solution. 2Ag" + Z(t) — 2Agls) + Zn Ag beg Za" 426 Za: E=-076V #0 (-0.76) 0.059, 12a") Eau Sev Office.: 606 , 6” Floor, Hariom Tower, Circular Road, NEWTONC Ranchi-1, Ph. 0861-2662629, 9696608612, 0607619968 LASSES.NET ) PREVIOUS YEAR CH ADVANCI JEELECTROCHEMISTRY |JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] ‘As the value of equilibrium constant is very high so the reaction moves in forward direction completely. [Ast from a) = VIO = 10 UC Keg = 10" = (ARTIC 10100 7000 39. Suppose the solubility of AgBr in 10"? AgNO; is S mol L* Aa Agee AgNO, —* Ag’ NO; (S+107)M. Ag" in 100 mil of solution = =10% mol I2x10*=($+107) (=S+10°S S410°s-12x10=0 On solving Mt Hence, [BF] =3% 107 M=3% 107» 10°! =3 x 10m" Tag T= Gx 107 + 10°) M=4x 107 10m? 24 10m BNO3] Nae = 3104x8108 a! 41046 10° Sm! = 246107 Sa! x107S ar! ro Kar + Rag + By; (Specific condvtvity of solution) 24107 + 2410747 10°) $m 35x10? Sm! = 55 Sm" (in terms of 107 Sm) 606 , 6” Floor, Hariom Tower, Circular Road, Ranc! 4, Ph.; 0651-2662623, 9836608812, 8507613968 NEWTONCLASSES.NET a