EXAMPLES Example 3.1 Represent the cell in which following reaction takes place : ‘Mg(s)+2Ag* (0.0001 M) —=*Mg?* (013 M) + 2Ag(3) Calculate Eee if Eze =+ 3.17 Ve Solution: The cell may be represented as Mg(s)| Mg?* (0.13 M)|| Ag* (0.0001 M)| Ag(s) ‘The cell reaction may be given as, ‘Mg(s) ——> Mg?* (0.13 M) + 2e7 2Ag* (lO M) + 2e7 ——> 2Ag(5) Mg(s) + 2Ag* (10 M) = Mg”* (0.13 M) + 2Ag(5) (n=2) 2 yagi? Me AB __O13*t 935.18 [Mg] [Ag* J G07) ‘According to Nemst equation e on 0.059 =Et- login @ 2.96 Example 32 Calculate the equilibrium constant for the reaction, Gu (5) + 2Ag* (aq) Cu (ag) +248 (8) Eq =+ 0.46 V Solution: We know, stor | 222 x= Anilo| 22] ston (2%048 ~ Antes 0059 | = 3.92 x10! Example33 The standard electrode potential for Daniell cell is 1.1 V. Calculate the standard Gibbs free energy forthe reaction : Zn(s)-+Cu2* (ag) === Zn?* (aq) +Cu(s) (A1SB 2013) Solution: We know, : AG? = n=2 for the given reaction F =96500C, E°=+41.1V from equation (i) AG? nFE? i) 2 96500 «1.1 = 2123003 Example 3.4 Resistance of a conductivity cell filled with 0.1 M KCI solution is 100 ohm. If the resistance of the same cell when filled with 0.02 M KCI solution is $20 ohm, calculate conductivity and molar conductivity of 0.02 M KC! solution. Conductivity of 0.1 M KCl is 1.29 Sm", We know, Solution: Conductance x Cell constant C x Cell constant Cell constant = 1.29 100 m™* = 129m" = 1.29 em For 0.02 M KCl, R=520 ohm Conductivity = Conductance Cell constant % Cell constant 1 3 gly EL x1.29= 2.48 «107 oh 1 a ohm! ex = 124S cm? mol! Example 3.5 The electrical resistance of a column of 0.05 M NaOH solution of diameter 1 cm and length 50 cm is 5355 x10° ohm. Calculate its resistivity, conductivity and molar conductivity. Solution: Area of cross-section = nr? =3.14% (0.5)? om? = 0.785 cm? We know, Rapxt a 3.55 x10? =p x 20 0.785 Resistivity, p= 87.135 ohm cm ‘Conductivity, u = 0.01148 Sem 35 Molar conductivity Ajq can be calculated as, Ag =n x 1000 M 7 = 0.01148 x 1008 05 2, = 229.6 S cm? mol” _ Example 3.6 The molar conductivity of KCI solutions & different concentrations at 298 K are given below : Amol L") AglS om? mol” 0.000198 148.61 0.000309 148.29 0.000521 14781 0.000989 147.09 . ‘Show that a plot between Ap, and CY? is a straight line Determine the values of \‘y and A (slope) for KCl OO ——— Scanned with CamScannerjon: Squate f00t Of concentration and corresponding slain ance are tabulated ahead : ‘om bu ee CUA Ly? Ag /Sem? mol”! 0.01407 148.61 0.01758 bes 0.02283 14781 0.03145 " 14705) A plot of Am against CY? is given below : 1498 149.4 1490 © 005 .010 015 .020 .025.030 .035 or Kou)" It can be seen that it is nearly a straight line. From the intercept (CY? =0), we find that ‘Nin =150.0S em? mol“ A=~ slope = 87.46 § cm? mol“'(mo.~")". Example 3.7 Calculate Ain for CaCl and MgSO 4 using owing data Nejre = 119 Sem? mol x and 16.3 Sem? mol™* = 160 S cm? mol co 1+ = 106 Sem? mol hg? soF Solution: A‘, CaClz = Keys +2 ey =119 +2763 = 271.6 S cm? mol™ Ny MgSOq =2igg2 +20 5o2- = 106 + 160 = 266 S em? mol" Example 38 The equivalent conductances of sodium chlo- de, hydrochloric acid and sodium acetate at infinite dilution are 264, 425.9 and 91.0 S cm? mol”, respectively, at 25°C. Caleu- He the equivalent conductance of acetic acid at infinite dilution. ery Similar Question Calculate A° _ for acetic acid. Given that Aq (HCD = 426 S om? mol”! N°, (NaCl) = 126 Sem? mol”! 1° (CHyCOONa) = 91S om? mot (CBSE Delhi) 2010] "Solution: According to Kohlrauch’s la» G. R. Bathla Publications Pvt. Ltd., Delhi Ae catsc00%s = cu,coo- + Anna =hye Hhge Masia =hyge th ge = 1264 ‘Adding eqns. (i) and (i) and subtracting Rew,coo that thar thee 91.0 + 425.9 - 126.4 ce Aea,coo- tar = A= cHscoon = 3905 S cm? mol™ Example 3.9 The conductivity of 0.001028 M acetic acid is 4.95107 $ cm7!. Calculate its dissociation constant if \ for acetic acid is 390.5 S cm? mol”. tion: | We know, Solutio "gt , im ERX z Given : x = 4.95 x10™ S em “5 ,, 1000 ‘ ion (i) A = 4.95 X10 x From equation (i) Am x10 x Oe = 48.15 ohm™! cm? mol AG, _ 48.15 iat 1.1233 Degree of dissociation, = 7 = 5555 CH,COOH == CH,COO™ + H* 1=0 c 0 0 ea, Cae Ca Ca Dissociation constant, K = CH3COO™ WH" } {CH; COOH] _CaxCa_ Ca? =a ‘Substituting the values of ‘C* and* a’ in above equation, we get, = 0001028 x (0.1233)? 1- 0.1233, Example 3.10 A solution of CuSO 4 is electrolysed for 10 minute with a current of 15 ampere. What is inure ih current Of 5 ampere. What is the mass of copper =1.78x107> KE Solution: W= . where i=i/ 96500" : one. = H1SxO0K3175 5 635 96500 2 1.75, = 0.296 g ++ Mass of copper deposited at a mass) INTEXT QUESTIONS determined Potential of Mg2+ by forming a cell with <, Mg can be 5 standard hydrogen Mg (s)| Mg” 9 (0911 N91 Hy (atm Pr Scanned with CamScannerQ.2 Cam you store copper sulphate solutions ina Ans. Q.33 Consult the table of the standard electrode poter Ans. wm, ~ — Fxtg?*ntg ell Extente por? Eas jpq =—OT6V. Edt cy 2 HOV Since the standand reduction potential of Zn is legs than that of copper, hence, zine metal will reduce Cu?* ions: present in aqueous solution of copper sulphate. Thus, we can not store copper sulphate solution in a vessel of zine. Zn (3) + CuSOg (aq) === ZnSO4 (aq) + Cu Eason proves = EResced dex ~ EO siiedspecten = +034 (0.76) = 4 1.10 Positive value of E® confirms that above redox process is spontaneous and hence, we cannot stére copper sulphate solution in a vessel of zine. Is and suggest three substances that can oxidise ferrous ion under suitable conditions. Eggs pgs 240.71 V ‘Only those species can oxidise ferrous ions (Fe?*) whose standard reduction potential is more positive than 0.77 V. ‘Thus, suitable oxidising agents will be Fy, Cl, Bry Q. 34 Calculate the potential of hydrogen electrode in contact Ans. with a solution whose pH is 10. If pH of solution is 10 then its [H* ] ion concentration will be 107'° M. Let us consider a reduction half cell [}H* G07? My| Hy (atm) | Pt Electrode process : 2H* (07! My +2e~ == He (L atm) = Hel 1-10” ary poy? According to Nernst equation, ee . Le 0.059 (n=2) logQ log 10” =- 0.59 V Q.35 Calculate the emf of the cell in which the following reaction takes place : Ni(s)+2Ag* (0.002 M) == Ni?* (0.160 M) + 2Ag (5) Given that Egy) = 41.05 V ‘Ans. Reaction quotient of the given cell reaction will be : 2 ime org x08 (ast? (0.002) ci ra Sg +105 — oe Jog 4108 = +0914 Q..36 The cell in which the following reaction occurs; Be (ay) +21 (ay) —> 2Fe™ (aay 15 has Ey = 0.236 Vat 298 K. Calculate the standard free energy and the equilibrium constant of the rae” AG =~ nFE? im = 2% 96500 x.0.2365 — 45548 J =~ 45.548 1 i= anos] 5] 2% 0.236 0.059 Q.37 Why does the conductivity of @ solution decreases wi, dilution ? ‘ASB ang Conductivity of an electrolyte solution depends on i. number of ions present per unit volume. On dilution, te frumber of ions present per unit volume decreas therefore, conductivity also decreases. Q. 38 Suggest a way t0 determine the Kin value of water Ans. See article 3.8 (Page 179). Q.3.9 The molar conductivity of 0.025 mol L~* methanoic acid Ans. = Antilog 10% Ans. 46.1 8 em? mol”! , Calculate its degree of dissocitin and dissociatign constant. Given: Rye = 349.6 Sem? mot. e 2 mot”! and Nyggg- = 54.6. em? mol ‘Ans, We know, HCOOH == Ht + HCOO™ Ai, HCOOH = iy. #25 :co0- = 36964546 * 104.2 S cm? mol" Degree of dissociation ‘a’ may be calculated as, ‘Let us consider the ionisation of HCOOH. HCOOH == HCOO™ + H* 1=0 c 0. 0 ie c-Ca ca Ca Dissociation constant of formic acid may be calculated (HCOO™] fH") [HCOOH] _CaxCa _ Ca” “C-Ca Ima 025 x (0.114)? 10.114 = 3.667 x10 Scanned with CamScannerjg current of 0 ampere flows through a metallic wire 120 Sour, then how many electrons would flow through Are wire ? 05 x 2% 60x 60 me 16 x107 22.25 x10 11 Saggestalst of metals that are extracted electrolytically. ‘he metals like sodium, potassium, magnesium, calcium. {nd aluminium can be extracted electrolytically. yo Consider the reaction : Cr 07" +14H* + Ge —s 2Cr* 48420 hat is the quantity of electricity in coulomb needed to reduce 1 mole of Cr,07~ ? {mole Cr207” requires 6 mole electrons for reduction pa Required charge = 6 faraday 6 X 96500 coulomb 415 Write the chemistry of recharging a lead storage battery, highlighting all the materials that are involved during re~ charging. Ans See lead storage battery on page 207, 314 Suggest two materials other than hydrogen that can be wed as fuels in fuel cells. fos. Methane, Methanol. [q.15 Explain how the rusting of iron is envisaged as setting of an electrochemical cell? ° Formation of carbonic acid takes place on the surface of iron : HO(/) + COp (g)> HyCO, === 2H* +CO}- In presence of H ion, oxidation of iron takes place Fe(s) > Fe** (ag) + 2e7 ‘The electrons are used at other spot where reduction takes place 02 (g) + 4H" (aq) + 4e7 > 2H30(1) Overall reaction is : 2Fe(s) + Op (g)-+ 4H (aq) =" 2Fe™* (ag) + 2H,0(0) ‘Thus, an electrochemical cell is established on the sur- face. EXERCISE as ans A Arrange the following metals in an order in which they dis- place each other from the solution of their salts AL Cu, Fe, Mg and Zn. ‘al sat =~ 1.66 V, Ee, 2+ jc, = + 0:34 V, Ere ire =~ 044 Vs Eigg2+ yg =~ 236 Vs Sa ay =~ 016 V. "S. A metal with lesser standard reduction potential can displace the other metal from solution of its salt Mg > Al.> Zn > Fe > Cn Sites’ * 7 OP” Decreasing order in which a metal will displace ‘other from its salt solution. 32 Ans. 33 Ans, 34 Ans, Given the standard electrode potentials : 2.93 Vs Bigs gg = + 0.80 V; KK =+0.79 Vi oye yg Eng? 1a nee Eoysrcp = OTAY “Arrange these metals in their increasing order of reducing character. (AISB 2010) Lesser is the standard reduction potential, greater is the re- ducing chara sc creMe cK Depict the galvanic cell in which the reaction ‘Zn(s) + 2Ag* (ag) Zn* (ag) + 2Ag(s) wes place. Further show : which elecrode is negatively charged ? (i) The carriers of current in the cell. (iii) Individual reaction at each electrode. (AISB 2008) Galvanic cell is : Zn(s)|Zn7* |]AB* |Ag() (i Zine electrode will be negatively charged. Gi) Electrons are current carriers. Gil) Zn (s) —> Zn* + 207 2Agt + 2e7 —> 2Ag(s) () Calculate the standard cell potential E° , AG° and equi- librium constant of the following cell reaction 2Cr(s) +3Ca?* (5) == 2Cr** (ag) +3CA(s) 0.40 V. (ii) Calculate the standard cell potential E°, AG° and ‘equilibrium constant K for the following cell reaction : Fe?* (3) +Ag* (ag) == Fe** (aq) + Ax(s) Ebonics =+ 071 Vi Bice yy, =+0.80V Eos, =~ 0.74 V5 Boge yey ( Efedox process = EReduced species ~ EQxidised species Fost ica ~ Eo ice =- 0.40 - (0.74) =+034V AG® nFE° = 6 x 96500 x 0,34 a ~~ 196860 196.86 kI/mol K=Antilog [ nE® 0.059. . i) eathode ~ Esnode 0.80 - (+ 0.77) = 0.03 v —nFE® 1 96500 x 0.03 = 2895 J mot! = 2.895 kd/mol Equilibrium constant K = Antilog S| 0.059, = 10.03 = Antilog| ee] 3.274) Scanned with CamScanner38 Write down Nemst equation and emf of the following cells : ( Mg(s)| Mg?* (0.001 M)|| Cu?* (0.001 M1) | Cus) (ii) Fe(s)| Fe?* (0.001 M)||H* (1M) | Ha (@) (0 bar) Pes) (iii) Sn(s)|Sn?* (0.05 M) || H* (0.02 My | (8) (1 bar) Pr(s) (iv) Pt(s)| Brp(D| Br™ (0.010 M)|| H* (0.03 M) [H2(g) (bar) Pe Given + B5,26j5q =~ O18 Vs Eye, = Vs Ebr =*109VE Bear jg, =+034 V: O44 V5 Biggs yg =— 2.37 V. Ans Festres ~ Engng =034~ (2.37) =2.71V Anode: Mg(s) —> Mg”* (0.001M) + 2e7 Cathode : Cu?* (0.001 M) + 2e~ + Cu(s) ‘Mg(s)+Cu?* (0,001 M) == Mg?* (0.001 M) + Cu(s) (n=2) ‘According to Nernst equation Bae ogy 0 a2 22 tog =21V HH ~ Fpet* ire = 044) = + 0.44 V Anode : Fe(s) —> Fe** (0.001 M) + 2e~ ‘Cathode : 2H* (I M) + 2e~ —> Hp (1 bar) |M) + Ho (bar) (n=2) Gi) Ey Fe(s)+2H* (1 (Fe) [Hy] _ 0.001 x1 001 arp 1 According to Nernst equation E=E- 298 ogo =044— oe Jog 0.001 = 0.5285 = 0.53 V (ii) Egon = Ezanode ~ Etoode =0-(0.14) = O14 Vv Era Chemist GRB New 1 C689 Pa. Blectrode process : Anode : ‘Sn (s) —> Sn?* (095 yy $2 Cathode : 2H* (0.02 M) + 267” —> Ha (a) ‘Sn(s) + 2H* (0.02 M) = Sn?* (0.05 M) +H (gy t (Sn? J{H2]__0.05x1_ {snjfH* 10.02)? = 125 ‘According to Nemst equation E=E— on logio @ 14-292 togias 078 V (iv) Een = Eeatnoae ~ anode = 1.09 =~ 1.09 V Electrode proces: Anode : 2Br™ (0.01M) —> Bry +2e7 Cathode : 2H* (0.03 M) + 2e~ —> Hp (g) 2Br~ (0.01 M)+ 2H" (0.03 M) = Hy(@) + BRO t 1x10" 0 )By] bat [BrP ra (0? x (0.03) According to Nemst equation 0.059 2 0810 2 =~ 1,99 — 2.059 ae log (1.1 x10") =-129V 36 In the button cells widely used in watches and other de- vices the following reaction takes place Zn(s) + AgO(s)+Hy0(1) —> Zn* (ag) +2Ag(3) + 20H (aa) Determine AG® and E° for the reaction. Ans. Zn(s) —> Zn™* + 2e~ E°=-0.16V ‘Ag20 + HO + 2c” —> 2Ag+20H” E°=+0HV Econ = Ecatnode ~ Esnode 34 ~ 0.76) = 1.10 V ‘nFE® 2x 96500 x1.10= 4G" 2.123 x108 3 3.7. Define conductivity and molar conductivity for the solution ofan electrolyte. Discuss their variation with concentration. ‘Ans. See text on page 179. 3.8 The conductivity of 0.2 M solution of KCI at 298 K is 0.0248 § cm". Calculate its molar conductivity. 1000 1000 Ams. Ag = x22 ~ 09248 x 1000 M 02 = 1124S cm? mol! Scanned with CamScannervesiance of a conductivity cell containing 001 M ration at 298 K is 1500 ohm. What is the cell con- vty of 0.001 M KCI solution at 298 K is Vp (ASB 2008) The xctsol cat ifthe conduct g.1a6 x10™> Sem awe knows i) ars x =C Cell constant x =0.146 x107 § cm™ =4 = ohm™ R putting these values in equation (i), we get 0.146 «10° = x Cell constant 1500 Cell constant = 0.219 om™! 410 The conductivity of sodium chloride at 298 K has been de- tennined at different concentrations and the results are given below : 3.1 0.001 | oo10 | 0.020 | 0.050 | 0.100 Concentration /M 1237 | 118s | 23.15 | 55.53 | 106.74 ot xx/sm 7 Ans. Calculate Aq for all concentrations and draw a plot be- tween Ag and C12, Find the value of Nn. sus, All the required informations of the questions are tabulated. below = Concentra tion (C) (mot (oon 1.237 x10 10° x 0.001 ee 001 ost | 1.237 x10" Cot oo10 oa Janss x10?) 11.85 x10? 10° X01 O18 Baz 0.020 23.15 x10 oat 23.15 x10? 10? 0.02 ous ‘Ans. 5553x107 10° x 005 0.050 0224 | 55.53 x107 oun 2 106.74 x10" _ 9.0107 10? x0. 106.74 xi 010 0316 Gi Plot between Ag, and CY? Extrapolation of graph to-zer0 concentrations gives. tho value of AY, = 0.0125 m? mort ‘nit om? mat") 0.0100) 0 0.05 0.10 0.15 0.200250:300:35 : C7 ott 9 Conductivity of 0.00241 M acetic acid is7:896 x10~* Som", Calculate its molar conductivity if X, for acetic ‘acid is 390.5 S cm? mol™!, What is the dissociation con- stant of acetic acid ? 1000 = -s 1000 hg 2100057896 10° > Seppe = 32,763 § cm? mol” 3278 = 0.0839 HCOOH — CHCOO” + HY to ° leg ca 0.00241 x (0.0839)? _ 1.69610" 10.0839 09161 1,85 x107 How much charge is required for the following reduction ? (1 mole of AP* to Al, (1 mole of Cu* to Cu, (id 1 mole of MnOg t0 Btn?*. @ Abt + 327 —> al Reduction of L mole Al?* requires 3 mole electrons. < Charge on 3 moles electrons = 3 x 96500 coulomb 289500 coulomb or I mole of electrons carry charge = 1 faraday 3, moles of electrons will carry charge =3 x1=3 faraday cu + 2° — cuts) Reduction of 1 mole Cu* requires 2 mole electrons. Charge on 2 moles electrons = 2 x 96500 coulomb 193000 coulomb or 2 faraday Scanned with CamScannerGR) MeO gs HHT 6 Se + Mn? Prom Paraday’s first lew tn + 4n,0 ak Bieta Picea al oe 15717108 Redaction of 1 mote MoO; requires $ mole electrons ch Charge on S motes electrons = $ + 96800 comers 637 ve = 482800 conlom = 144 min cS farnday From Faraday's second law : MAS How much electricity in terms of faraday it required to Exe #0512 Cate aa Ets Pepaivaert mass) (1) 20 & of Ca from motten Cols (750 198) - Atari ag 40 of Al from molten A130 isa 1998) Eng “10811 (Es) Ams (1) CaCl; —+ Ca? 6 207 | (Mohen state) 108 Ca 6 2 4 (Resection) asia 1 mole calcium (40 g) requires 2 mole electrons, ie..2 ‘ faraday for redaction as 20g calcium will require | mole electrons, ie. | faraday foe reduction i) 1:0, MABE, 2AV* 5 30% Pe AV 6 dem sa Wry = 0436 8 “1 mote aluminium (27 g) requires 3 mole elecwons 317. Predict ifthe reactions between following ae fea faraday) 3 (i) Fe®* (aq) and I~ (aq), (i) Ag” (aq) ard Ca, 4p alumina wil euie = » 40 fray for reduction (iii) Fe** and Br~ (aq), (iv) Ag and Fe™ (as), = 4.44 faraday (0) Br3(aq) and Fe** (ag). AIM How much electricity is required in coulomb for the oxida- ws wae vm sel sion of (a) | mole of HzO 10.03 and (b) 1 mole of FeO to Given = Ep yp = | Fe ca = ’ Fe;0,? = ating 2+ O80 V, ‘Ans. (a) The oxidation reaction is ter SUP Eagriag = +08 Exo pe = + 0.71 H,0 —+ 10, + 2H? + 267 Fe Fe a 1 te 2 Pre ‘Ans. A redox reaction is feasible if its E° is postive Q=2xF (i) Fe** (ag) +1 (aq) == Fe? (ag) +41 = 2. 96500 = 193000 coulomb 2 (b) The oxidation reaction is: Ejpedox = EReduced species ~ EQuidised species FeO+ 51,0 — 3 F205 +H er = Eb ~ Ear Q= F = 96500 coulomb =0.7-054=+0.23V (Feasible) BAS A solution of Ni(NO 5) is electrolysed between platinum (ii) 2Ag* (ag) + Cu ==* 2Ag(s) + Cu lectrodes using a current of ampere for 10 minute, What A P 4 Etesox = Eitedeced wecien ~ ESxisncd esis ‘mass of Ni is deposited at the cathode ? oom ond Ans. Weknow, W= ME _ ,5420%0 «58.712 grep = Exgtiag ~ Fou 1c ee 96500 96500 = 0.80 - 0.34 = +046 V (Feasible) : ee electrolytic cells A, B, C containing solutions of . - 2+ (oq) + LB ‘ZnSO 4, AgNO y and CuSO 4 respectively are connected in a le aa series. A steady current of \.5 ampere was passed through Ejtedox process = EReduced species ~ EQridised speci them until 14S g of silver deposited at cathode of cell B. . BES pte — Eby ree How long did the current flow ? What masses of copper a ast) fe aid snc swetPhdeposicd ? = 0.77 - 1.09 =~ 0.32 V (Not www.bathlabooks.com Scanned with CamScannergecvochomistry Ant + Fe™* (aq) => Ag* (aq) + Fe?* (aq) Ejtosox. = EReduced species ~ Ere et “ABT IAB =0.77-0.80 =-0.03 V (Not feasible) v LBry (aq) + Fe®* (aq) —=* Br- (aq) + Fe** (aq) Ffedox = Etedued species ~ ESxidned species = Ebene ~ Eb pes = 1.09-0.77=4032V (Feasible) Predict the products of electrolysis in each ofthe following : \i) An aqueous solution of AgNO ‘An aqueous solution of A trodes \H0 A dilute solution of H 20 4 with platinum electrodes 8) An aqueous solution of CuCl, with platinum elec- trodes ‘5. i) AgNO. ith silver electrodes 18NO3 with platinum elec- 3 (29) —> Ag* (aq) + NO3 (aq) H,0 == H¥ (aq) + OHT (ag) At cathode : Ag* ion is reduced because standard reduc- ‘ion potential of Ag* is greater than H* ion, 2Ag* + 2e” —4 2Ag(s) (Reduction) At anode : Oxidation of Ag takes place at anode : Ag ———> Ag* + e° (Oxidation) i) If inert electrodes, i-e., platinum electrodes are used in electrolysis then Ag* is reduced at cathode and OH ion is oxidised at anode. ‘At cathode :Ag* +e” —> ag At anode : 40H” —+ 2H,0+0, +2e~ ity H2SO, —> 2H* +soy- 1,0 = H* + oO At cathode : 2H* + 2e” —+ Hy (Reduction) At anode : 40H” —+ 2H0+ 0, +2e" (Oxidation) Discharge potential of OH™ ion is greater than that of SO” ion, thus OH” ion is neutralized at anode. (i) Cucly —+ cu* 4 2c1- 1,0 = HY + on aeguthode = Cu2* ion is reduced at cathode since stan- dard reduction potential of Cu?* is greater than that of H™ ion. Cu? + 26° As anode : Cl~ ion is oxidised at anode since discharge Potential of CI” ion is greater than that of OF- 20 ay + 26° (Oxidation) Scanned with CamScanner|, Multiple Choice Questions (Type-l) Which cell will measure standard electrode potential of copper electrode? (a) Pt(s)] Hg, 0.1 bar)] H* (ag., 1M) || Cu?* (ag., 19) | Cu (b) PU(s)|H(g.1 bar)| H* (ag.,1M) || Cu?*(ag., 2M) | Co | (6) Ps Hag. 1 bar)] H* (ag., 1M) |}Cu?*(ag.,1M)| Cu (@)PA(s)| Hp(g.1 bar)| H* (ag., 0.1M) || Cu* (ag., 1M) | Cu | 2. Electrode potential for Mg electrode varies according to the o 0.059 1 | uati hig = 4 equation Egg = Egg de agg] graph of Eygg2+jyyg YETSUS log [Mg”* Jis : 1 t @é£ wrt pea a E toaima? | toglmg?] = ! Ae os _/ @e iN i : toaleng*] —~ togimg] = i Which of the following statement is correct? (@) Egy and A,G of cell reaction both are extensive properties (0) Egg) and A,G of cell reaction both are intensive properties (©) Ecay is an intensive property while A,.G of cell reaction is an extensive property (8) Eze i8 an extensive property while A,G of cell reaction is an intensive property / difference between the electrode potentials of two ' lectrodes when no current is drawn through the cell is ! “alled : | (@) cell potential (by cell emt (© potential difference (4) cell voltage Which of the following statement is not correct about an jnert electrode in a cell? (a) It does not participate in the cell reaction (b) It provides surface either for oxidation or for reduction reaction we (0) It provides surface for conduction of electrons (d) It provides surface for redox reaction \An electrochemical cell can behave like an electrolytic cell ‘when ¢ + ey (b) Ecott > Eexy =0 (a) Eceit Ey AE (©) Een > eet ct fe ‘of the statements about SolvONS Of lect, 9% 10. nL 2. 1 @) ct 1B. 15. jot correct? {a) Conductivity of solution depends upon size fio {b) Conductivity depends upon viscosity of solution {c) Conductivity does not depend upon solvation of iy, present in solution ty of solution increases with te (d) Conduct mperature Cues the data given below find out he strongest eng a gent. ° Fe opice BY Fayre “HBV ° e1s1V E24, =-074V ‘MnO, /Mn?* CeCe @cr cr cr @ Mn Use the data given in Q. 8 and find out which ofthe following is the strongest oxidising agent. @cr (b) Mn?* (©) MnOj (a) Cr?* Using the data given in Q. 8 find out in which option tie order of reducing power is correct. (@ Cr+ Nats); y= -201V hy) yO) > O4(g) +41" (aq) +407; ES = 1.23-V oot (a $e —9 iad: Fey, = 0.00 V a) CV (aq) foi re : By = 1.36 V |. Multiple Choice Questions (Type-Il) | In the following questions two or more options may be correct. 18, The positive value of the standard electrode potential of Cu?* (Cu indicates that: (a) this redox couple is a stronger reducing agent than the 1° Mz couple (©) this redox couple is a stronger oxidising agent than HYVH (c) Cu can displace Hy from acid , (d) Cu cannot displace H from acid 19. E24 for some half cell reactions are given below. On the basis of these mark the correct answer. (ANH (ag) +e” —> Fie); E2y =0.00V (B)2H,01) —s 03(8) +41" (aq) +407; £24 = 1.23 V (C)280F" (aq) —+ $20} (ag)+2e" ; E%y = 1.96 V (@) In dilute sulphuric acid solution, hydrogen will be reduced at cathode (b) In concentrated sulphuric acid solution, water will be ised at anode (¢) brdilute sulphuric acid solution, water will be oxidised ‘at anode (4) In dilute sulphuric acid solution, $03- ion will be oxidised to tetrathionate ion at anode 2, a = 14 V for Daniel eel, Which of the following expressions are correct description of state of equilibrium in et Lake 222 agg, (©) ok, = 22. (8) og K = 1.1 0.059 21. Conductivity of an electrolytic solution depends on : (2) nature of electrolyte (b) concentration of electrolyte 2. (6) power of AC source (d) distance between the electrodes Ajglt2O is equal to: (a) ®rparicry + Nie n01t) ~ Ane ac (6) A pcttvoyy + Nit st0y) ~ Nine rot (©) Krarinoy) + Nncraonty = Are xasto,) (A) Nparatory + Nneticy ~ Niner gery What will happen during the electrolysis of aqueous solution of CuSO, by using platinum electrodes? (a) Copper will deposit at cathode (b) Copper will deposit at anode (cy Oxygen will be released at anode (d) Copper will dissolve at anode What will happen during the electrolysis of aqueous solution of CuSO, in the presence of Cu electrodes? (a) Copper will deposit at cathode (b) Copper will dissolve at anode (c) Oxygen will be released at anode (d) Copper will deposit at anode Conductivity x, is equal to : Gt (bo) S* OF rt Ra L (c) A, (d) — © Am Os Molar conductivity of ionic solution depends on : (a) temperature (b) distance between electrodes (©) concentration of electrolytes in solution (d) Surface area of electrodes For the given cell, Mg | Mg?* |] Cu2* | Cu (a) Mg is cathode (0) Cu is cathode (c) The cell reactior Mg + Cu* — Mg?* +n (@) Cuis the oxidising agent lll, Short Answer Type Questions (Type-itl) 28. 30. aI. 32. Can absolute electrode measured? Can Ege 0F A,G° forcell reaction ever be equal to zero? Under what condition is E,.y = 0 to A,G =0? What Potential of an electrode be oes the negative sign Eb? req =~O-TOV mean? Aqueous copper sulphate solution and aqueous silver nitrate solution are electrolysed by I ampere current for 10 minutes in separate electrolytic cells. Will the mase of copper and silver deposited on the ea same diferent? Explain your answer, = “MNO BE Same or Depict the galvanic cet Cu+2Ag*— in the expression Ml in which the cell reaction is Ag+ Cu? Scanned with CamScanner |‘M-_Value of standard electrode potential for the oxidation of CI” ions is more positive than that of wat sr, even then in the electrolysis of aqueous sodium chloride, why is CI” oxidised at anode instead of water? 3S. What is electrode potential? 36. Consider the following diagram in which an electrochemical cell is coupled to an electrolytic cell. What will be the polarity of electrodes ‘A’ and ‘B’ in the electrolytic cell? Salt bridge Solution ‘of ZnSO, (8) Electrode Electrolytic cell 37. Why is alternating current used for measuring resistance of an electrolytic solution? 38. A galvanic cell has electrical potential of 1.1 V. If an ‘opposing potential of 1.1 V is applied to this cell, what will happen to the cell reaction and current flowing through the cell? 39. How will the pH of brine (aq. NaCl solution) be affected when it is electrolysed? 40. Unlike dry cell, the mercury cell has a constant cell potential throughout its useful life. Why?) 41. Solutions of two electrolytes ‘A’ and ‘BY axe diluted. The pm of ‘B’ increases 1.5 times while that of A increases 25 times. Which of the two is a strong electrolyte? Justify your answer. 42. When acidulated water (dil. H,SO4 solution) is electrolysed, will the pH of the solution be affected? Justify your answer. 43. In an aqueous solution how does specific conductivity of electrolytes change with addition of water? Which reference electrode is used to measure the electrode potential of other electrodes? 45. Consider a cell given below Cu] Cu2* [| CI” | Clp, Pt Write the reactions that occur at anode and cathode 46. Write the Nernst equation for the cell reaction in the Daniell cell. How will the E,,y be affected when concentration of Zn?* ions is increased? What advantage do the fuel cells have over primary and secondary batteries? 44, 47. Gro newer roy HOSS Hp 48, Write the cell reaction of a lead storage batery discharged. How does the density of the ef ae a ‘when the battery is discharged? ote. 49, Why on dilution the Ay of CH;COoH iy, drastically, while that of CH3COON increases pat IV. Matching Type Questions (Type-tv) y 50, Match the terms given in Column I with the unig Column I. os Column T Cotte ty os [(?) [Sem [Een (o_o 5 (@ |Sem?mort Jol lolos io |v / —_| 51. Match the terms given in Coluran I with the items gies Column I. 7 ————_ Column 1 (Cofaran I Oa (p) |intensive propery | wlegy lq) |éepends ca emia 2 ions/volume lolx __ o) lextensive propery (oa, Gean [increases with nts ‘52. Match the items of Column I and Column I Column 1 (Cotuma It | (a)[tead storage battery |ip) [maximum eficieacy | [(0)| Mercury cett (a) [prevented by gatvaisicn (o) Foe cet (o)_|ives steady portal (@|Rusting (3)_|Pb is anode, PbO> is cabot | 53. Match the items of Column 1 and Column I. Column 1 Cotuma 11 cafe lo [exe JOO) Am, @) JA, 1X, ofa lo x a IQ is) |G* Rg 54, Match the items of Column I and Column IL Column 1 Column It (a)|Lechlanche ceit[() ce reaction 2H, + 0)—? 2° Scanned with CamScannerctrochemistry [fm[NrCa cell [lq [does not involve any ion in solution oN land is used in hearing aids, [Fuel cel (@) [rechargeable (ap[oMercary cett (3) reaction at anode| [zn —> zn?* + 26 (© Jeonverts energy of combustion int] electrical energy 8, Match the items of Column I and Column II on the basis of data given below 2 7 V, E° “35 V, B24. = 14 Fie 287M Ey Feu a ce 09 V Fon (Be Column 1 Column tt of (e) [meta is the strongest reducing agent Om (q) |meta ion which isthe weakest oxiis| ing agent Jofau (© |non metal which is the best oxidising lagent (oe (6) [unreactive meta (olan (© Janion that can be oxidised by Au? jo fur (w) Janion which is the weakest reducing agent (of (%) [metal ion which isan oxidising agent Assertion and Reason Type Questions (Type-V) (@) Both assertion’and reason are true and the reason is the correct explanation of assértion, (©) Both assertion and reason are true and the reason is not correct explanation for assertion. (©) Assertion is true but reason is false. (@) Both assertion and reason are false. (©) Assertion is false but reason is true 56. Assertion : Cu is less reactive than hydrogen. 2 is negative. Reason! £8 ae, '8 HeBAL Assertion : Egey should have a positive value for the cell to function. Reason: Ecathode < Eanode $8, Assertion : Conductivity of all electrolytes decreases on dilution. Reason: On dilution number of ions per unit volume decreases. 89. Assertion : A,, for weak electrolytes shows a sharp increase when the electrolytic solution is diluted, Reason : For weak electrolytes degree of dissociation increases with dilution of solution. : 6. Assertion : Mercury cell does not give steady potential, Reason: In the cell reaction, ions are not involved soluti 61. Assertion : Electrol anode instead of Oy Reason: Formation of oxygen at anode requires over voltage. 62. Assertion : For measurin, and AC source is used. lysis of NaCl solution gives chlorine at Tesistance of an ionic solution Reason : Concentration of ionic solution will change if DC source is used. 63. Assertion : Current stops flowing when Ey = 0. Reason : Equilibrium of the cell reaction is attained. 64. Assertion = E,,.,,, increases with increase in concentration of Ag* ions. Reason : Eq... has a positive value. 65. Assertion : Copper sulphate can be stored in zine vessel. Reason : Zinc is less reactive than copper. VI. Long Answer Type Questions (Type-VI) 66. Consider the figure and answer the following questions. Salt bridge (A) Electrode —|— }— (B) Electrode Cells (@) Cell ‘A’ has Bay =2 V and cell ‘BY Ecey) = 1.1 V which of the two cells “A” or ‘B’ will act as an electrolytic cell Which electrode reactions will occur in this cell? (i) Heel “A” has Bgay = 0.5 V and cell "BY has Egey = 1.1 V then what willbe the reactions at anode and cathode? 67. Consider the figure given below and answer the t0 (vi) given below. questions Silver plate Ag? (aq) Zine plate © w Scanned with CamScannerin of electron 3) Redraw the diagram to show the direct flow. Gi) Is silver plate the anode or cathode? Gi) What will happen if salt bridge is removed? iv)When will the cell stop functioning? (¥) How will concentration of Zn?" ions and Ag’ ions be affected when the cell funi 1. Multiple Choice Questions (Type-!) /@ 26 © 40 5 1.) 13.) 14d) 15. (a) I, Multiple Choice Questions (Type-H!) IK (bd) (oe) (be) 2 G@B) 22. (acd) IV. Matching Type Questions (Type-IV) 50, (41), bs), =p), (Ia) 52, (a), (b—1), (=p), (a) 54, (9), (b—0), (—p.), (da) IV. Assertion and Reason Type Questions (Type-V) 56. (c) ‘$7. (c) 58. (a) ‘59. (a) 60. (3) |. Multiple Choice Questions (Type-!) |. Potential of an electrode when the electrode is reversible with the ion at unit concentration and at 1 bar and 25°C. = o 059 1 2 Bag? mip = Emig ye 9) ee | ° 9 2+ Fxg? ng = Eup neg tg 08M | y c++m x The plot of Eyyg2+ y4p against log [Mg7* ] will be straight fine with positive stope and intercept. 3. Ecqu isan intensive property while AG of cell reaction is an ‘extensive property. Intensive property does not depend on the amount of substance present in the system 4. Cell emf = Potential difference between the two electrodes ‘when no current is drawn through the cell. 6. Electrochemical cell when recharged, acts as electrolytic cell. The condition for recharging is: Eeexiemat > Ecett 7. Conductivity of ions in electrolyte solution depends on solvation of ion, ANSWERS = ~wanay uipitow will the concentration f Zi?” toms and ays he affected after the cell becomes “dear? ; ship between Gibbs fr ais the relationship CE energy oy a sotion ina galvanic cell andthe emf of the cx." ym work be obtained from a galvanic cell re will the maximut a 2 2) % Oy 16.6) 17 @) 2 fac) fab) 25. (ab) He). ey 51. (as), (bp). (a) (IF) 53. (as), (b—1). (a). (IP) 55. (a1), (b=). (CV). (EV, (68). a). (8—v.0) 6.) 2) OH) BCrfs) 9 Cr+ 4307 Eq Ci(s) is strongest reducing agent. Greater is the negatne value of standard reduction potential, more isthe redoing character. 9. MnO3 +8H* +5e~ —> Mn?* +4H,0 Exmoyntats =4151 Greater is the positive value of standard reduction potest. stronger is the oxidising agent. 10. Mn?* Mn2* +4H,0 (Suble) Cr(s) is strongest oxidising agent hence it will giv stable ion in its oxidised form. Crs) — Cr?*(ag.)+3e7 (Stable) 2-00 Scanned with CamScanner‘on electrolysis give aluminium at eathode Molten, 9413+ 4302 Al203 — Site 34 4307 catnode Al +3e7 —> Al snode sie aluminium 20% —> Op +47 i n requires 3 mol electron i.e., 3 faraday chase’ 7 cell constant = between two electrodes wea of electrodes dipped in solution stant remains constant for a conductivity cell fes reverse reaction to that of discharging cell co Charging involv process sO, will reduced to Pb at anode. Xan co) *Amcns0H) ~Amnsc 2 [higNHG 42° C+D gNa™ +4,0H7] = [NyNat $24,010] 2 [NgNHG +2 OH” J= AigNH,OH 1. (i) 200 — 02(g) +4" (eq) +4e~ Egy =+1.23V (Expected reaction) «crag $chiore Eig) =+136V (Actual reaction) Reaction (ii) takes place jnstead of (i) because of over potential of Op and high concentration of Cl ttipte Choice Questions (Type |) 18 Foti HOM Eiji, 79% : Cu?* /Cu is stronger oxidising agent than HT Hy cu2* #267 —9 CH) Jace H from acids. ‘Thus, copper cannot displace Hz, * +SO4" , 1,804 —? 24 H,0—=H" +0” ut +267 > He 2,010 — Olt ,_2.303RT jogo 2 nE fs at jae call Cathode Anode We know, 9) +4 (ag) +4e~ E=E (1) ‘At equilibrium, given E?= LV, From (1) o= _2.308R7 jogio K 2F m1. 2, 26. 27. 2.303RT F 0.059 logyg K = 2.2 Conductivity depends on, nature and concentration of electrolyte solution. Agito) = Neaitcr + acnsont ~ArntNsc my logio K =. ou Similarly, Natgo) = Ancnsos) + Arncnsotty ~ Aintsnon Aygtjo) = msiory + Arata) ~ ented ‘CuSO, (ag) — Cu 2+(aq)+ SOF (aq) HO H*(aq) + OH (aq) Cathode Cu?* +2e7 —> Cu ‘Anode 20H" (aq) ——> H,000+5 0x18 4267 's solution of CuSO, is electrolysed using When aqueou! wed at anode and copper electrode then copper is dissol copper is deposited at cathode. Anode : Cus) —> Cu +207 Cathode: Cu2* +2e7 —> Cuts) x 0 mle x u where G* ell constant 1 BlnRl- oie ‘Molar conductance of an electrolyte solution depends on temperature and concentration of electrolytes in solution. Copper is cathode in following cell : Mg(s)| Mg?" |}cu2* | Cuts) Anode: — Mg(s)—— Mg?* +2e7 Cathode: Cu?* +2e7 —> Cu je: Cu +26 Ma(s) +Cu** —> Mg** +Cu(s) I Short Answer Type Questions (Type!) 28. 29. 30. No, absolute electrode potential of an electrode cannot be measured. No, E* and AG? for cell reaction can never be 270 G*= FE? vis never zero hence, AG will also be not equal 19 22r0. A cequilbrium ce,, when the cel is completly discharged. Eze =0 and AG=0 AG =-nFE when E'= 0, AG is also equal t0 zero. Scanned with CamScanner32. 36. 37. 39. “40. 41. a2. 0.76 V Negative shows that the reducing power of zine is greater than that of hydrogen, Zn +HS0,—> ZnSO, +H w=—iE__1x10x60%3175 96500 96500 ‘Mass of silver will be different because the equivalent mass of Ag is different. Cus) | Cu?* |] Ag* | Ag(s) CI” is oxidised at anode instead of water because of over Potential of oxygen and high concentration of chloride ions. Tendency of an electrode to gain ot to loose electron is called electrode potential. (A) Negative polarity (B) Positive polarity Direct current causes the electrolysis of electrolyte solution hence its concentration changes, thus we do not use direct current for measuring the resistance of electrolyte solution. When, Even = Eexternal then no current will flow through the circuit. Aqueous solution of brine contains Na* , cr, Ht and OH™. Electrode process are given below : 2H* +2e°—> Hy (Cathode) 2Cl”- —> Cl, +2e (Anode) Remaining solution will contain NaOH, which is base, therefore, pH will increase. Electrolyte is not consumed in the cell process of mercury cell hence it will deliver the current at constant potential throughout its life. Electrolyte “B’ will be strong electrolyte because it is completely ionised and on dilution the molar conductance ‘will increase to the small extent due to increase in speed of ions only. PH of solution will not be affected because there is no change in the concentration of H* ions. At anode : 2H, 0() —> 02(6)+4H" +4e7 At cathod 4H* +4e7 —> 2H, T Specific conductance of an electrolyte solution decreases ‘on dilution with water because number of ions per unit volume decreases. Standard hydrogen electrode is used to measure the electrode potential of other electrodes. The given cel is : Cu(s)|Cu* |] CIm [Cer Anode: — Cu(s) —> Cu* +2¢> Cathode: Clz(g)+2e” — 21" 46. Daniell cell Zn(s)|Zn?* || Cu2* | Cu(s) - orem, Zn(s) —> Zn™* +26> Anode + Cathode: Cu* +2e7 — Cu(sy Cell reaction 2a(9)+ Cu 20 eG) (Zn?*} [cu*] . zn? Eee = Bean ~ 72 og 20] [cu?*) Above equation shows thatthe cell potential wi with increase in the concentration of Zn 2 jgy “8 Fuel cell is environmental friendly cel. It does recharging like those of secondary cells. Futue tS vehicles will be drives by fuel cells. Fein 48. Discharging process of lead storage battery is: PO(s) + PbO (8) +2804 aa.) —> 2P6S04(0) 42104 Sulphuric acid is used as electrolyte in this cell, is discharged, the density of electrolyte solution because H,S0, is consumed while water is producag Molar conductance of CH COOH increases rapid because its degree of ionisation increases, CH;COOH+ H,0 = CH;COO™ (aq) +1,0° Sodium acetate (CH3COONa) is strong electrolyte, itis completely ionised. Molar conductance of sodium aca ‘gradually increases on dilution due to increase in set of ions. VI. Long Anwer Type Questions (Type-VI) 66. (i) Cell ‘B’ will act as electrolytic cell because potential of ‘B’is less than that of “A”. Electrode process inthe cl‘ may be given as Zn™* +2€" —+ Zn(s) (cathode) Cu(s) — Cu* +2e° (anode) i) Cell ‘BY at higher potential wil act as galvanic ell. he electrode process may be given as, Anode: Zn(s) —> Zn?* +267 Cathode: Cu?* +2e7 —+ Cu(s) (i) The cell is : Zn(3)|Zn7* || Ag* |Ag Electron will flow from zinc anode to silver cabs! ® external circuit . Gi) Silver will act as cathode, since its standard rede Potential is greater than that of zinc. ey iii) Potential will drop to zero if salt bridge is suds removed. be (iv) Cell will stop functioning when it is discharged! when cell potential is zero. (v) Nest equation for the cell is : 47. When ci 49. o7. Scanned with CamScanneree P @ ga gr 0089 tz") (vi) When cell is dead or discharged then E will be zero and ~ log the cell will he at equilibrium. Then, concentration of Za ?* 2a? ) potential will decrease with increase in concentration and Ag* will not change 68, The required relations are Zn7* | while it will increase with the concentration of A AG = -nFE aed Ww, ‘nme = NEE where £ = Cell potential E” = Standard emf of the cell Scanned with CamScanner