ELEcTRo CHEM ak GALNANIC CELL Half Celis Mereuty-mercuri¢ oxide-hydroxide Ton half-cell In this half-cell, a pool of mercury is covered with a paste of solid HgO and a solution of a base. ‘This equilibrium reaction that takes place at the platinum electrode is qa Hg0(6) +H,O(1) + 2e- = He(1) + 201-aq) + Sy Expression of Reduction Potential < 7 RT. dS Fourie Fourpeonte pow Quinhydrone Electrode Q Quinhydrone is the name given to the molecular crystal formed between quinone (Q) and ; hydroquinone (QH,). When dissolved in water, th crystal decomposes into its constituent compounds = x The reduction reaction at the electrode is OH Cums Q 0 oH ‘The quinhydrone electrode consists of a spiral of gold wire immerses in the solution whose pH is to *® determined. The solution is saturated with quinhydrone, The reduction potential of the electrode is ® « given by RT. ay Faia “Eoin aR Ne ~() : avhere Fog ne bas a vac of 0.699 6V. le e onAAG ee At v avait ee ov ia lt am We aR : m 2.303 S06 FR eae eB = or & "he quinhyerone electrode can be coupled with a reference electrode to form a cell Reference electrode ior (),Q, QH, | Au ‘and its omf is determined ‘experimentally, We have Bam By -B, Fy 2303RT 1p oe ea catia “PB Hence pH = ~ 2.303 RT/E AL298 K, have Be gra Ban Bag Se a on) Limitation of using Eq. (3) The linear relation between electrode potential and pH of the solution (Eq, 2) holds good only up to ‘certain pH value (= up to 8.5). Beyond this pH, the relation is no longer linear as may be seen from the following considerations. ‘The hydroquinone is a weak acid and it dissociates in a stepwise manner as shown below: (HQ) WQS H +HO ie (4,0) =—— HIG) Hy Ha aa ~ ‘Mass balance expression gives (HQ = [HO] + (HQ 1+ 1041 6 The [HQ] and [are related to [H,Q] through the equilibrium constants K, and K, Ths ig K,H,Q) , KKH) e HALO Me rior, OT or a ) (HT + KE ]+KK, ~@) fr) wy eaeconcentrations. Substituting the concentration of QH, from Eq, (8) into Eq. (1), we get RT AN OR {H,Q), (QL T +K KK, 0 Glass Blectrode ‘The glass electrode consists of a glass tube terminating ina thin-walled bulb A as shown in Figure A special glass of relatively low melting point and high electrical conductance is used for this purpose. The bulb contains a solution of constant hydrogen-ion concentration and an electroxle of definite potential, Usually cither silver chloride electrode dipped in 0.1 mol dm? solution of hydrochloric acid or a platinum wire inserted in a pH 4.0 buffer solution containing a small quantity Of quinkydrone is employed, The bulb is inserted in a solution whose pH is to be determined. The ‘esulting half-cell is combined with a reference electrode (say, for example, the calomel electrode) through a salt bridge. This entire assembly constitutes a cell which may be represented as Ag|AgCi(s)|0.1 mol dm *KC!| Glass | Sotution of unknown pH|Calomel electrode... (10) The emf of the cell is given by By7B,-B, qy here E, is the reduction potential ofthe reference electrode and E, is that of the rest of uit, ie. AglAgC\s) [0.1 mol dmv? HCl | Glass | Experimental solution of unknown pH... (12) ‘The value of E, is experimentally found to be dependent on the difference of pH of solutions on cither side of glass. Since pH of the solution within the bulb remains constant, the potential E, depends on pH of the experimental solution, This dependence is given by CS RET Since the solubility of serail low, the il of Q and QH, may be replaced by their < « b « ~ & § 8 S S ‘ ‘ ‘ 4 sme(3)Fon tat ede Foalsat, ee a NE peels CIE) | Arey Where 2, is the activity of hydrogen-ions in the experimental solution. The standard reduction poseafial of the glass electrode is usually determined experimentally as all pss electrodes do not have the same value. For this, « buffer solution of known pH is taken and the glass electrode is dipped into this solution and the emf of the cell (Eq. 10) is determined. From this emf, E.,. can be determined as follows: 2.303RT rie SSO Ey ‘ , Thus Ble = Eassad Bay 2.303RT a P id ‘Afr this, the glass electrode is dipped into the solution whose pH isto be determined and then pH is calculated with B5,. gound above. The theory of glass electrode has been explained on the basis of the transfer of hydrogen ions through the glass. The potential set ‘up at the glass-solution interface is analogous to junction potential between two solutions containing hydrogen ions, the value of such a potential is given by RT, a Sitti ee Ee(-t,.)5 a (14) where a, and a, are the hyirogen-ion activities of outer and inner solutions, respectively. Since in the glass electrode only hydrogen ions can move across the boundary, we have t_=0 and t,, =1 nS} Thus, Eq. (14) reduces to Since a, is constant (inner solution), it follows that RT E=constant - | tn , 2.303RT or E=constant + F pH wn (16) Equation (16) is identical in form with the experimentally derived Eq. (13). Limitations of Glass Electrode Because of the high internal resistance of the glass electrode, which may amount to as much as 100 million ohms, ordinary potentiometers cannot be used to measure emf of cell Instead, special vacuum, ‘tube potentiometers are employed. With the glass electrode, it is possible to measure with an accuracy of about 0,000 5 volt or 0.01 pH unit,| (TT The glass clectrode can be used up to pH.9. It is unaffected by poisoning and oxidizing and reducing agents, If the solution pH is greater than 9, particularly when sodium ions are present, the experimentally obtained. pH value is usually lower than the true value. This is probably due to infiltration of sodium ions into the glass lattice, However, new glasses have been developed, with which pH range can be extended up to 13 or 14 Itestration: In a cell consisting of glass electrode in solution with pH of 7.0 and a calomel electrode, the ‘emf of plass electrode at 298 K was 0.062 V. When a solution of unknown pH replaced the ‘standard bufler, the glass electrode potential was 0.145 V with the glass clectrode negative. Calculate the unknown piT if during caliberation, the glass electrode was (a) negative and (b) positive. Solution: (a) Glass electrode as the negative terminal. The emf of the glass electrode at 298 K is given by E gus = Ebas + (0.089 13V)pH where E;,,. is constnat, Its value can be determined from the given data that E,, = 0.062 Vat pH=7. Thus Ee = Eye ~(0,059 13V) pH = 0.062 V-(0.059 13 V) *7=-0.352V ‘Thus when E,,.= 0.145 V Tim Fie) _ O.145V+0352V _ gy mH TOs OOsIaV | (6) Glass lectrode as the postive terminal Here Byun 000620 Therefore Ey = Eyas ~ 9.0591 13V. pH =~ 0.062.V ~(0,059 13 V) 7 =-0.476 V Es ~Ejon) _ 0.145 +0.476V _ FARADAY’S LAWS OF ELECTROLYSIS: @ Faraday’s First Law : ‘. hen an ele caren pasion a leat he amount of substance deposited is proportion to the quantity of electricity passed through the lectrolyte, If be the mass ofthe substance deposited bypassing Q coulomb of charge then according tothe @ law, we have the relation : woe Q : § ‘A.coulomb is the quantity of charge when a curent of one ampere is passed for one second. Thus, ‘ , Hense PA Sosp3y ~ O0smIaV < x K fs amount of charge in coulombs, Q-= Current in amperes * time in seconds =Ixt —7Ca | Baars 2 constant, knownas electrochemical equiva, ani th characterises ofthe substance deposit ‘When a current of one ampere is passed for the one second, ic, one coulomb (Q= 1), then wz Thus, electrochemical equivalent can be defined as the mass of the substance deposited by one coulomb of charge or by one ampere of eurrent passed for one second, fi) Faraday’s Second Law When the same quantity of charge is passed through different electrolytes, then the masses of different Substances deposited atthe respective electrodes will be inthe ratio oftheir equivalent masses, The law can be illustrated by passing same quantity of electric current through three voltameters Containing solution of H,SO,, CuSO, and AgNO;,. In the first voltameter, hydrogen and oxygen willbe liberated in the second, copper willbe deposited and in the thd silver wil be deposited. PP ND DAD DTD DED Mass of hydrogen Equivalent mass of hydrogen Cues Mass of copper ~ Equivalent mass of copper It is observed that by passing one coulomb of electric charge, : H, evolved = 0,00001036 g: Cu deposited = 0.0003292 g and Ag deposited = 0,001118 ¢ > These masses are in the ratio oftheir equivalent masses, From these masses, the amount of electric 4 charge required to deposit one equivalent of hydrogen or coppet or silver can be calculated, : 1 . ee sca : For hydrogen = 5 oapzaz =96500 coulomb : This follows that 96500 coulomb of electric charge will deposit one gram equivalent ofany substance. . 96500 coulomb is termed as one Faraday and is denoted by F. > Again according to first law, ; weZxQ Ze, } > yee SL Z=B/96500; 7-7 Fundamental unit of charge ‘As one g-equivalent of an ion is liberated by 96500 coulomb, it follows that charge carried by one p- equivalent of an ion is 96500 coulomb. If the valency of an ion is ‘n’, the one mole of these ions will carry a charge of nF coulomb, One g-mole of an ion contains 6.02 * 173 ions, nF Then, the charge catried by an ion = ¢ p> "1923 coulomb nF Forn=1, The fundamental unit of charge = § 99 , 19% 96500 Z eg 49 i eae 1.6 * 10" coulomb or — Lcoulomb = — 6.25 10!* electrons ‘The rate of flow of electric charge through a conductor is called the electric current.jciemacapey | | GBalieih 1 coulomb = ampere-second Electric current == Hee one _ Leoutlomb 1 second Volt is a unit of electrical potential difterence, itis defined as potential energy per unit charge. joule __I newton x 1 metre Teoulomb {ampere x 1 second Electrical energy = potential difference * Quantity of charge =V*Q =Vx1xt= Watt -second (I= ampere; t= second) One faraday is the charge required to liberate or deposit one gm equivalent of a substance at corresponding electrode. I volt = IE We kx = = as feknow = w 7Q =Zit =p +O where Z = — Bi96500 ‘Equation (i) is used to calculate the mass of solid substance dissolved or deposited at an electrode. tv, For the gases, weuse V= goo Ail) where V = volume of gas evolved at S.T.P, at an electrode V,,= Equivalent volume = Volume of gas evolved at an electrode at 8.7.P. by 1 Faraday charge Table | S.No, Metallic conduction Electrolytic conduction f Electric current flows by Electric current flows by movement of electrons. ‘movement of ions. ; Tons are oxidised or reduced at 2 tll ‘No chemical change ithe elect 3 It does not involve the transfer | It involves transfer of matter in| of any matter the form of ions, ‘Ohm's law is followed Resistance decreases with increase of temperature Product of electrolysis ; In case two or more type of positive and negative fons are present in ‘solution, during clectrolysis certain ions are discharged or liberated at the electrode in preference to others. In general, in such competition the ions which is stronger oxidising agent (high value of —— i: 28-877, Tia Sul, New {17, Neue Khas, New J Heb: wenichenacademy in re ddddugaaunasATLL D LLU LL AEE E EAP E LETTS «+ North Delhi: 72, Mall Rosd, GLB. Nagar, New Dethi - 110008 » South Delhi LT ll standard reduction potential) is discharged first at the cathode, The increasing order of deposition of few cations is ‘eceming order of depo Similarly, the anion which is stronger reducing agent (low value of standard reduction potential) is liberated first at the anode, The increasing order of discharge of few anion is: S027, NO5.087. Br Tnceiing order of isctosing ‘Thus, when an aqueous solution of NaCI containing Na”, CF, H* and OH” ions is electrolysed, H fons are discharged at cathode and CI ions at the anode, ie., His liberated at cathode and chlorine atanode. ‘When an aqueous solution of CuSO, containing Cu’, $O,2-, H* and OH’ ions is electrolysed, Cu?" ions are discharged at cathode and OH" ions at the anode. Cu* + 2° —+ Cu (Cathodic reaction) 40H" —+ 0, + 2H,0 + 4e" (Anodic reaction) Cu is deposited on cathode while O, is liberated at anode. Thermal of metallic oxides » The thermal stability of the metal oxide depends on its clectropositive nature. As the electropositivty decreases from to top bottom, the thermal stability of the oxide also decreases from top to bottom. The oxides of metals having high positive reduction potential are not stable towards heat. The metals which come below copper form unstable oxides, ic, these are decomposed on heating. Ago H+ 2g + 1/20, Heo > 2Hg +0, Bad Naz0 | No decomposition AiO; CONDUCTANCE Introduction: Both metallic and electrolytic conductors obey Ohm’ law ie, VIR where V = Potential difference in volt; = Current in ampere ; R = resistance in Ohm. We know, resistance is directly proportional to length of conductor and inversely proportional to ross sectional area of the conductor. i Rock op Fr ( p= Specific resistance ) Specific resistance is the resistance of a conductor having lengttis of 1 cm and eross sectional area ‘of lcm’, es Unit of R is ohm and unit of specific resistance is ohm om. B/7, Jia Sarai, Neer IFT, Hae Khas, New Dethi 110016,» 25. O11-41415514, 0916597284, Toll-Free 180-200-4940, Wee: nchensemtlen:inlectrolyte. It is denoted by ». A=exV (+ = ober! car! x cm? = oar! ca?) Usually conceatration of electrolytic solution is expressed os C gm equivalent per litre. me c ' {Volume heving 1 gm equivalent electrobe in the solution} Thus, amex 2 Molar Conductance Molar conductance may be defined as conductance of an electrolyte solution having 1 g mole" electrolyte ima litre. It is denoted by A, Ag=K*V Usually concentration of electrolytic solution is expressed as ‘M” g mole electrolyte per litre. 1000 V=o— M Hewce, ack Relation between Aand A: A= 0% A Onsager expression for strong electrolytes Ag = Az -(ANS +B)” 6 { Reciprocal of resistance is called as conductance and reciprocal of specific resistance is called as specific conductance. : i nL A eS == R=p.— C=-.— C=n— vos "2s pt i where C = conductance (ohm) ; K = specific conductance (ohmr‘cm™') Miho and siemens are other units of conductance 1 K=Cy (Wa = cell constant) Specific conductance= Cell constant x Conductance ‘Specific conductance is conductance of 1 cm’ of an electrolyte solution. in case of electrolytic solution, the specific conductance is defined as the conductance of a sohution of definite concentration enclosed in a cell having two electrodes of unit area separated by 1 cm apart Equivaleat conductance is the conductance of an electrolyte solution containing 1 gm equivalent of ‘ The frst tem AA Je is the decrease in moar conductivity due tothe asymmetric effect. 5 ‘The second term Be is the decrease in molar conductivity due to the electrophoretic effect. x Relation between ionic mobility snd conductance ; aoe. ; ; mene | ee “ . Dethi: 28-B7, Sin Sarai, Near HT, Hauz Khas, New Web: my. As01 TAN ASIII * Mae feel hel CS (on EXERCISE I Single Correct Type Standard Electrode Potential of a cell (E,,.) y North Delhi. 72, Mall Road, GTB, Nagas. New re 36597244, Toll Fee: 1800-20-40. ‘The standard reduction potential at 298 K for the following baif cells: E'= Zn" |Zn=-0.761V 5 = Cr" |Cr=-0.740; E z= , 8 , Bore =070 Which is the strongest reducing agent? (=) Zils) (&) Crs) He @FeMaq) ‘The standard E"_ values of A, B and C are + 0,68 V, -2.54 V, -0.50 V respectively. The order of their reducing power is (@)A>B>Cc ()A>C>B (@)C>B>A (QB>C>A RT The Nernst equation, E=E*-— = In. Q indicates that the equilibrium constant K_ will be equal to Qwhen RT @E=E" oF! (E=ze10 @)Ee=1 Ifthe Ey for a given reaction hs 0 negative vale, which gives the correct relationships forthe values of AG" and K,,? (0) 4G>0,Kqg<1 (0) AG">0;K.>1 (©) AG<0:Kq >t (8) AG' 1,000; BP=H1.23V Fe" +2e > Feta), E°=-044V AG? (in 1d) for the reaction is @)-%6 32 (2 (@-16 ‘Anaquedus shin containing one mole perlite each of CuNO,)> AgNO; Hg,NOJy MENO:)2 is being electrolysed by using inert electrodes. The value of standard potentials ae Eis “DOV Egg “OV: Feces = O3AV and Ey tings =23V With increasing voltage, the sequence of deposition of metals on the cathode willbe (a) Ag, He, Cu, Mg (b) Mg, Cu, Hg, Ag (©) Ag, Hg, Ca (d) Cu, Hg, Ag “The standard reduction potential valves of three meaic ction, X,Y, Z are 053,304 and 1.48 V respectively, The order of reducing power of the coresponding metal is (a)Y¥>Z>X (XYZ (@Z>Y>Xx (@Z>X>¥ Neat IT, Haw Kiss, New (Delfi 110016 © Ms ON-A1AISS14, 091 “wom chemacaders. lilt — ‘Delhi - 110009 + South Delhi: 28-B7,AF Ls | TTT 8 Electrode Potential of a cell (E,,) B Given Eiainy =-237V, Epos) =W1.66V Evo, =~0.23V which of the following statemont is INCORRECT (a) Mg will reduce both Ni’? and AI"? to their respective metal (b) Mg will reduce only AI"? to Al and not Ni*? to Ni (c) Al will reduce only Ni‘? to Ni and not Mg"? to Mg (d) Mg’? solution can easily be stored in the aluminium vessel ‘The equilibrium constant for an electrochemical reaction, 2Fe” +Sn®* <= 2Fe" +Sn"* is (E*(Fe* /Fe’*) =0.75V, E*(Sn** /Sn®) =0.15V,(2.303RT/F) = 0.06V) (a) 10" ¢b) 107° (©) 10 (@ 10” The standard potential of a Daniel cell is +1.10 V and the equilibrium constant for the cell reaction is 1.5 * 10", It can be concluded that (@) Zine oxidises copper (b) Displacement of copper by zine goes to near completion (©) Copper oxidises zine (@) Displacement of zinc by copper goes to completion Saturated solution of KNO, is used to make salt-bridge because (a) Velocity of K* is greater than that of NO, (b) Velocity of NO; is greater than that of Kt (©) Velocity of both K* and NO; are nearly the same (d) KNO, is highty soluble in water KCl is used in salt bridge because (a) It forms a good jelly with agar-agar _(b) itis a strong electrolyte (6) it isa good conductor of electricity (4) the transference umber of K* and Cl ions are almost equal For a cell constructed with Cu|Cu’* anode and Ag’ | Ag cathode at 25°C. Calculate the cell potential at 25°C, [Cu**]=0.3 Mand [Ag']=0.05M. —Ef,.,, =0.34V; Eig = 0-80V (a044Vv. (oat y (040V (@o34v The cell potential for the following electrochemical systemn at 25°C is Al] Al?*(0.01M) | Fe”*(0.IM)| Fe (@)123V ())121V (@L2V ()+2.19V Bey =—H66V; Bing, = H044V 28-197, fia Sari, Near iT, Hau Khas, Ney Heb: wechemacademyin » ppp ppt fll lltltllT9| noma EL > ASS TTS For the concentration cell MM? (aq, 0.01 mol dar) || M* (ag, 0.1 mol dar) |M the EMF (E) of the cel t a temperature (I) equals RT RT Ru ce RT @ 2308-- 230 (© Fhe #23085 (0 Beye =? 308 16. The standard emf of a cell, involving one electron change is found to be 0.591 V at 25°C. The TT equilibrium constant of the reaction is (F = 96500 C) (a) 1.0 « 10! (b) 1.0 = 108 (©) L0« 10" (d) 10 «10 117. _ EMF of reduction hydrogen electrode in term of pH is (ot 1 atm pressure) : @ Ex, =e. pH (Es, a i Ey =* ee CT xpH (4) Fu, =-0.0591pH s 18 Ifthe pressure of H, gasis increased from | atm to 100 atm keeping H” concentration constant at | CS 'M, the change in reduction potential of hydrogen balf cell at 25°C will be (a) 0.059 V. (6) 0.59:V (c) 0.0295 V (d) 0.118 V 19, The reaction U2 Hy(g) + AgCl(s) + H(aq) + Chi(aq) + Axts) ‘occurs in the galvanic cell (@) Ag/AaCI@)KCKSoIn)/AgNO,|Ag —_(t)PUH,(g)H1C\oIn|AgNO ,0In) Ag (© PUH(@)HICIGoIn/AgCI/Ag (€) PUH(@)KCHsoIn)/ABCI)AR 20. Consider the following Galvanic cell. ors cue) x0) Es is ‘Anode Cathode By what value the cell voltage change when concentration of ions in anodic and cathodic compartments both increased by factor of 10 at 298 K (@) 40.0591 (b) 0.0591 (c) 0.1182 @o 21. The EMF of the cell. Pt(s)| H, (1 atm) |H* (a=x)| [A (@= 1) | HL (1 atm) | Pts) et hw a7 rt (atm) Pt at 25° is 0.59 V. The pH of the solution is x ait @! (4 @7 {a 10 22, The standard reaction Gibbs energy for the electrochemical reaction 1,0} + 2Fe-+14H" > 2Cr* +2Fe” +7H,0 is-793 kT mot. Calculate the standard cell potential (@)4137V O4A1V (42.74 (42.059 Delhi - 110016 * Ph: O11-41415515, 091 ‘Tol Free: 1800-21 whew chemercnieos ia ria + North Delhi: 72, Mali Road, GTB. Nagar, New Delhi - 110009 » South Delhi: 28-57, fia Sarai, Near IF, Haue Khas, New| - oD 23. Ifthe H concentration is decreased from 1 M to 10M at 25°C for the couple MnO, /Min®, the the oxidising power of the Mn0,,/Mn* couple changes by ()-0.18V (6) 0.18 (038 @-038V 24. Consider the call Casa"? (1.0 M/C? (1.0 MY/Cufs). If we wanted to make a cell with a more positive voltage using the same substances, we should (2) increase both (Cd"?] and [Cu*?] to 2.00 M (b) increase only the [Ca°?} to 2.00 M (€) decrease both the [Ca] and [Cu] to 0.100 M (@) decrease only the (Ca°?} to 0.100 M 25. Consider the reaction of extraction of gold from its ore 1 : ‘Au+20N"(aq.) + 70, (g) + 9 Hj0—> AU(CN); + OF Use the following data to calculate AG® for the reaction Ky {Au(CN);} =X 0, + 2H,0 + de" — 40H3E° = + 0.41 volt Auw*+3e = Au; EP=+ LS volt Aut +26 Aut; P= 41.4 volt (a)-RT inX + 1.29F ()-RTMX-2.11F 1 ()-Rlia 5 +21F (@)-RTinX~1.29F 26. For the EMF of a hydrogen electrode to be zero, the pressure of hydrogen required in neutral pHlis (a)1*107 atm (b) 110" atm (0) 1.0 atm. (4) 0.0 atm 27. If the ratio of composition of oxidized and reduced species in electrochemical cell, is given as (@E-E 28. The correct value of E°, of a half cell in the following graph of E. vs log m{molality) is: @oc”ac (AB (BB @cc ppp ttre LOSS STIS IST NAREecrochenity] 29. The correct Nernst equation for the concentration cell: Pt] H,(P) |HCK(a,), | AgCIG)| Ag || Ag] AgCi(s)|HCI(a, ) H,(p)|Pt | without liquid junction would be > > | Rese a ned. =EE ih = 2 “es Ea, > _2RT, (a), RT, (eh > © Brae ey OFF ay 30. Which is correct Nernst equation for redox reaction O+ne<2R? + RT, {0} [0] ter ey aE OR” [o_ fee) (o_ Ben Onn? Ws 31. Consider the cell; ZnlZn** (a =0.01) || Fe** (a= 0.001), Fe* (a@=0.01) | Pt ‘eat~ 1-71 Vat 25°C for the above cell. The equilibrium constant for the reaction: Zn+2Fe™ = Zn* +2Fe* at 25°C would be close to (107 (b) 108 (©) 10" (10° 32. For the cell reaction, Sn(s) + Su** (aq) = 2Sn?*(aq), separate electrode reactions could be written with the respectively standard electrode potential data at 25°C as ‘Sn*¥(aq) + 2e-> Snag), B= 40.15 V Sn** (aq) +2e-—> Sais), B*=-0.14V. When RT/F is given as 25.7 mY, logarithm of the equilibrium constant (in K) is (26 (b) 226 (6)2.26 (@) 2.26% 10" 33. Aconventration cell wth two hydrogen electrodes at two different pressures is depicted as Ei oe: L(ai(Pt) bEEELELTTTVY, The potential (E_,) of the cell is pat OF oe nk ow OF eae Oo Py 3, Dtsch dca dasdsoncamscsnovinuae ieibicas ress Calculate the cell EMF in mV for Pe | H,(latm) | HCI(0.01 Mp | | AgcKs) | Ag(s) at298 K if AG? values are at 25°C ks ~ 109.56 <3 for AgCl(s) and ky ~ 130,79 mot tH’ + Ch) (aq) (a) 456 mV (b) 654 mV (c) 546 mV (d) None of these Consider the cell Ag(s)/AgBr(8)/Br (aqlAgCls) | Ct (aq)| Ag(S) at 25°C. The solubility produet Constants of AgBr & AgClare respectively'S x 10- & 1 x 10° . For what ratio ofthe concentrations of Br’ & CF ions would the emf of the cell be 2er0 (@)1:200 (b)1: 100 (©) 1500 (@) 200: 1 The molality of (NH,),SO, solution that has the same ionic strength as 1 mol kg solution of KCI is @) 13 molkg! —(b) 12 molke’ —_(e) 2/5 mol ky (6) 3/5 mol ke For a 1 molal aqueous NaCl solution, the mean ionic activity coefficient (y,) and the Debye- ‘Huckel Limiting Law constant (A) are related as (@) logy, =V2A (0) logy, =-V2A(@) y, = 10" (7, =10* An aqueous solution containing 0.01 M FeCl, and 0.06 M HClO, has the same Ionic strength as a solution of (a) 0.09 M NaCl (b)0.04M Na,SO, (¢)0.06M CuSO, (4) 0.03M HPO, Faraday laws of Electrolysis 47. 48. 49. Four moles of electrons were transferred from anode to cathode in an experiment on electrolysis of water. Total volume of the two gases (dry and at STP) produced will be approximately (in litres) (224 (448 (9672 (90.4 During electrolysis of an aqueous solution of sodium sulphate, 2.4 L of oxygen at STP was liberated at anode. The volume of hydrogen at STP, liberated at eathode would be @12L (247 ()26L @4sL During the electrolysis of AgNO, (using Pt. electrodes) concentration around cathode as weil as anode fills from 4 M3 M. What will heppen if this happened with Ag electrodes (@) result will remain same (©) concentration around cathode will fll from 4 M to 3 M but around anode will increases from 4 MtoSM (©) reverse of statement *b’ (@) concentration increases from 4 M to 5 Mon both the electrodesLS | TITTY 50. $1, 53, 54, 5S. $7. 58. When the electric curront is passed through a cell having an electrolyte, the positive ions move towards cathode a nogative ions towards the anode. If the cathode is pulled out of the sotution (a) the positive and negative tons will move towards anode {(b) the positive ions will start moving towards the anode while nogative ions will stop moving, (6) the negative ions will continue (o move towards anode while positive ions will stop moving (d) the positive and negative ions will start moving randomly Of the following metals that cannot be obtained by electrolysis of the aqueous solution of their sats are (a) Ag and Mg, (b) Ag and Al (©) Mg and AL (a) Cu and Cr Which of the following statements is true for an electrochemical celt? (@) Reduction occurs at H, electrode (b) H, is cathode and Cu is anode (©) H, is anode and Cu is cathode (a) Oxidation occurs at Cu electrode Blectrochemical equivalent of an element is ‘Atomic weight Valeney Atomic weight «96500 96800 0 valency Atomie weight valency x96500 (©) Vateneyx96500 ‘When an aqueous solution of lithium chloride is electrolysed using graphite electrodes (a) Cl, is liberated at the anode, (b) Lis deposited at the cathode (c) as the current flows, pH of the solution around the cathode remains constant (d) as the current flows, pH of the solution around the cathode decreases. ‘The electric charge for clectrode deposition of one gram equivalent of a substance is (a) one ampere per second (b) 96,500 coulombs per second (6) one ampere for one hour (d) charge on one mole of electrons ‘One gm metal M'? was discharged by the passage of 1.81 * 10°? electrons. What is the atomic weight of metal? (a) 33.35 (b) 133.4 (0) 66.7 (ass ‘The density of Cu is 8.94 g env. The quantity of electricity needed to plate an area 10 em * 10 cm to a thickness of 10°? em using CuSO, solution would be (a) 13586 C ()2712.C (c) 40758 C (a) 20348 During electrolysis of an aqueous solution of sodium sulphate, 2.4 L of oxygen at STP was liberated at anode. The volume of hydrogen at STP, liberated at cathode would be (@12L (b)24L (2.6L (@)4gb During electrolysis of an aqueous solution of CuSO, using copper electrodes, if 2.5 g of Cu is deposited at cathode, then at anode (a) 890 ml of Cl, at STP is liberated (b) 445 ml of O, at STP is fberated (0) 2.5 g of copper is deposited (4) a decrease of 2.5 g of mass takes place 7 gp tA A ALSfSfUSHALUIV I RRAAAAARAR REIbald . ment b—b—b—bb bb Lb | | B60. The charge required for the oxidation of one mole Ma,0, into MnO] 2 2° a 67. presence of alkaline medium is {Sx 9SSVOC —_W) 94SODC (10 96500 (296500 ‘When an aqueous solution of lithium chloride is electrolysed using graphite electrodes (2) Cy, is berated at the anode. {b) Lis deposited at the cathode {©) as the current flows, pH of the solution around the cathode remains constant | (ds the current flows, pH of the solution around the cathode decreases, Two Faraday of electricity is passed through a solution of CuSO,. The mass of coppet deposited at the cathode is (at mass of Cu = 63.5 u) (oe O58 (28 @ 1272 Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 mA current. The time required to liberate 0.01 mole of H, gas at the cathode is (1 F = 96500 C mol") @)9.65 * 10's (b) 19.3 x 10's (28.95% 10's (d) 38.6 x 10*s Pure water does not conduct electricity because it (@) bas low boiling water (0) is almost unionized fo) is earl (4) is readily decomposed ‘Which one of the following statements is correct? With dilution, the equivalent conductance of (2) Both strong and weak electrolyte decrease (©) Strong electrolyte increases while that of weak electrolyte decreases (©) Strong electrolyte decreases while that of weak electrolyte increases (@) Both srong and weak electrolyte increases Equivalent conductance of 0.1 M HA(weak acid) solution is 10 ScnPequivalent“ and that at infinite Gdution is 200 Scamequivaleat“' Hence pH of HA solution is @13 @17 (923 (@37 If xis specific resistance of the electrolyte solution and y is the molarity of the solution, then “,, is gen by 1600x aT ‘The resistance of 5 M solution of an electrolyte in a cell was found to be 50.Q. Ifthe electrodes in the cell are 2.2 cm apart and have an area of 4.4 cm? then the molar conductivity (Q'S oF mot) of the solution is 02 Woo (90.002 (@) None ofthese ‘The dissociation constant of n-butyric acid is 1.6 10° and the molar conductivity at infinite i 380 « 10 Sm*mot. The specific conductance of the 0.01 M acid solution is (@) 152» 10% Sor? (b) 1.52% 107 Sur! (c) 152% 109 Sar (4) None x bso am 102 OF ® i00 oyeee=———eaaeaeaeaeaeeeeee—xX— + North Dethé: 72, Mali Road. GTB. Nagzz, ‘Debi - s20076 « PR: GLi-4D41S514| | 70. 7 76. 77. 8, the eqparraiens ccmbucsonce of The ionization constant of a weak electrolyte is 25 * 10* while che white bitin 0.01 M solution is 19.6 S cnr eq'. The equivalent conductance of the eke (in 'S cm? eq" ) will be (a) 250 (b) 196 (32 Which of the following curve represents the variation of 2, with Jé & ‘Which has maxmium conductivity : | (@)(CrONH), CL] )[CHONHL), CLIC (@) [CrONH). CIC, @) {CAHHJO, Molar conductances of BaCl,, H,SO, and HCI at infinite dilutions are 7,. 2, 208 %,, respectively Equivalent conductance of BaSO, at infinite dilution will be ] @ Berl gy kes |2G,+1,-%) © beet} z The specific conductivity of a saturated solution of AgCl is 3.40 10* ohms cx “25°C i, = 62.3 ohm em? mol & 4,, = 67.7 ohm” emi mol”, the solubility of AgC] a 25°C & (a) 2.6x 105M = (0) 45x 107M (0) 3.6 «107M (d) 3.6 10° The conductivity of a saturated solution of BaSO, is 3.06 « 10°* of’ cms’ aad &s equrvaeet x conductance is 1.53 ohar! cm equiv'. The K,, for BaSO, will be ‘ (a) 4% 10" (b) 2.5 «10° (6) 25 107 (a) 19* ‘ Molar conductance of 0.1. M acetic acid is 7 ohm“ cm mol . If the molar cond. of acetic acid at infinite dilution is 380.8 ohm’ cm? mol , the value of dissociation constant will be f (a) 226 x 10* mol dm? (b) 1.66 «10? mol dm ‘ (c) 1.66 x 107 mol dm? (4) 3.442.« 10 mol des ‘ ’ “The conductivity of a solution of AgCl at 298 K.is found to be 1.382 = 10° & cur’. The ionic conductance of Ag’ and Ct at infinite dilution are 61.9 01' ca mot’ and 76.3.‘ cm mol. | respecitvley. The solubility of AgCl is (@) 14% 10% mol L- (6) 1* 10% mol L* (@)1% 10% mol L* (6) 1.9» 10° mol L* In the electrolysis of an aqueous solution of a salt, the pH in the space near one of the electrodes increased. A solution of which of the following sats was electrolysed? (a) Cu(NO,), (b) CuCl, (KCl {@) None If'V,inthe equation A = sp. cond. x V, isthe volume ince containing | «3 of the electrolyte; V for a sun wl (c) 1000 cc {d) 10,000 ccn At infinite dilution, the eq. el of CH. ne HCI and CH,COOH are 91, 426 and 391 rio cr respectively at 25°C. The eq, conductance of NaCl at infinite dilution will be (in Sent eq") (a) 126 (&) 209 (c) 391 (a) 908 Calculate ,* (in § em? mo!) for NH,OH, given that value of ,* for Ba(OH),, BaCl, and NH,Cl are 523.28, 280.0 and 129.8 Sem mot respectively (a) 373.80 (b) 673.48 (c) 543.68 (d) 251.44 EXERCISE I Multiple Correct Type Which of the following is/are true for standary hydrogen electrode? (a) Temperature is maintained at 25°C (b) Hydrogen ion concentratin is 1M (©) Pressure of hydrogen gas is maintained at | atomosphere (d) It contains platinum metal which is used to adsorb hydrogen gas For the cell, Zn(s)| Zn** (aq) || Cu* (aq) | Cu(s) The cell potential E__, can be increased: (@) by increasing [Cu] () by increasing [Zn] (©) by decreasing [Cu”] (d) by decreasing (Zn*"] (Z —Weell potential of a galvanic cells negative then: (a) the cell reaction is non-spontaneous —_(b) the cell reaction is spontaneous (c) the cell reaction is exothermic (d) the cell will work in reverse direction A galvanic cell involves the following reaction, Zn(s)+2Ag" (aq) == Zn** (aq) +2Ag(s) Select the correct statements among the following (a) Zinc is negative charged (b) The given redox process is spontaneous (c)Ag' +e" Ag, takes place at anode (4) Zn(s) -> Zn?* + 2c, takes place at anode S- Given that, a a e Bae jpg =O-25V, Bape, =2034V; Ei... = 4080V, BY 2,,,, =-0.76V Which of the following redox processes will not take place in specified direction?” (8) Ni” (aq) + Cals) —+ Ni(s) + Cu?" (aq) (b) Cu(s) + 2Ag'(aq) > Cu"(aq) + 2Ag(s) (c) Cu(s) + 2H"(aq) > Cu*(aq)+H(g) (4) Zn(s) + 2H"(aq) -> Zn* (aq) + H,(g) & _ Inacell,2n(s) (Zn | H, (P0); the addition of H,SO, to the cathode compartment, will (2) decrease E (b) Increase E (©) Shift equilibrium to left (d) shift equilibrium to right a tS * Nocth Deli: 72, Mali Rod, GLB. Nagar, New as Saati Dele 25-007 ia Sagi Near, Haw Khos, Now| ooo? ae In which of the following cells: b, (a) Cuss) | Cu"* (0.01 M) |) Ag (0.1 M) | Agts) (b) Pe(H,) | pH = 1 |j Zn’ (0.01 M) | Zn(s) (©) PUGH.) | pH = 1 || Zn" (1M) |Zn(s) (d) Pr) | HW" = 0.01 M | Zn (0.01 M) | Zn(s), Pb(s)| PbSO, || PI, || Pb(s) 8 Sarted Saacet when San Which of the following expression represents the cell potential of above cell at 25°C? 0.059 Pb”* Janode (@ B=" f , 0.059. [Pot Janode_ [Pb janode (6) B= 619 pe? eathode 0.059, _-Ky(Pbl,) 0.059, (K,,PbI,/4)'" E=— ese Eo——| 2 (Poy Mn (FSO, gE MH aso, 9 Given: Ei = H0S4V; Fg = H.09V, BP a, = O44 Which of the following reactions are spontaneous? (@) Fes) +1, —>Fe* +21" (©) By +27) —32Br +1, (c} Fe(s)+Br, —>Fe* +2Br- (6) 1,42Br —921 + Br 10. _ In the following concentration cell, Ag(s) |AgCl (saturated) || AgNO,(aq) (1M)|Ag(s); K,Agcl= 1x10 the cell potential will be )Eg =2.96V (b) E,,,= 0.2955 V 1 gee ee a (8) Bag = Bog + 9 ig J ARC The tpt cate fst | Then: # cown 5), =, en st =-ate a owen 5), >0 then nFE > AH and it is endothermic reaction latte ke OP POH OD 2.9.9. 9.0-2-2-2-2-P-2f-2-f-f-f-f-EE | SCSI (©) When =) <0 then nFE < AH and it is endothermic reaction oe cee (3), =O, then AH > niFE and it is endothermic reaction In an electrolytic cel: (a) anode is positively charged (b) cathode is negatively charged (©) oxidation takes place at anode (@) reduction takes place at cathode If 9 gm H.0 is electrolysed completely with the current of 50% efficiency then: (a) 96500 charge is required (b) 2 « 96500 C charge is required (c) 5.6L of O, at 8. LP. will be formed (d) 11.2 LofO, at S.1.P, will be formed ‘One gram equivalent of a substance is liberated at an electrode by (a) 6.023 = 10° electrons {(b) 96500 C (©) 1 amp current for 1 second (d) 1 amp current for 96500 see The amount of substance liberated at an electrode is directly proportional to: (a) time (b) current (©) equivalent mass (d) resistance In a cell, Zn(s) [Za || H"| H, (Pi); the addition of H,SO, to the eatbode compartment, will (a) decrease E (b) Increase B (c) Shift equilibrium to left (@) shift equilibrium to right Which one of the following statements is(are) true regarding both galvanic and electrlytic cells? (a) In both cells, redox reactions take place (6) Inelectrolytic cells, a current is forced through a cell to produce a chemical change for which the cell potential is negative (c) In both cells, reduction takes place at the cathode (d) The ion flow through the salt-bridge in galvanic cell fs opposite to that flow in electrolytic cell EXERCISE III Subjective and Numerical Answer Type For the cell reaction 2Ce#*+ Co—+ 2Ce** + Co™* Big is 1.89.V. IPE? .,,., is~0.28 V, what isthe value of E° nee? Tie hs adie ache pvotal wt ikea e Cl, +2e —> 2Cr Given P2*+2C-—> Pt+Ch, Bey =-0.15V PR? + 26° —> Pt E°=1.20V Hf Big, = 0.52 V, Boyz = 0.34, what is Boy of the cell reaction Cu+ Cut —» 2Cur? memnenesA I ET Calculate the equilibrium constant for the reaction Fe + CuSO, = Given B® (Fe/Fe™*)=0.44V, E° (CwCu?*) =-0,337V. From the standard potentials shown in the following diagram, caloulate the potent Eh als By and E3 910525, pur 2454 Ly, UOTE 5 Calculate the EMF of the cell, a 2 Zn —Hg(c\M) | Zn?* (aq)| Hg — Zn(e,M) od at 25°C, ifthe concentrations of the zinc amalgam are: c, = 10g per 100g of mercury end + ©,= lg perl00 g of mercury . Calculate pH using the following cell : at a Pe (s)| H(1 atm) | H* (x M) || 1° (1M) | H, (1 atm) | PUGS) ifEpg = 0.2364 V. ua ft EMF of the cell Zn | ZnSO, (a, 0.2) || ZnS0,(a,) | Zn is -0.0088V at 25°C. Calculate the value o i The cell Pt, H,(1 atm) | H'(pH=x) || Normal calomel Electrode has an EMF of 0.67V at 25°C. qs Calculate the pH of the solution. The oxidation potential ofthe calomel electrode on hydrogen scale — TY is 0.28V. Consider the cell AglAgBr(s)/Br“JAgCl(s), Ag| Cl at 25°C. The solubility product constants of AgBr & AgCl are respectively 5 * 10-1 & 1 * 10-19 , For what ratio of the concentrations of Br = & CI ions would the emf of the cell be zero ? The pk, of Aglis 16.07. Ifthe B? value for Ag‘ Ag is 0.7991 V . Find the B® forthe bal eo reaction Agl (s) +e" Ag + F. LY fp pf 44 44, ppt f44-4- Determine at 298 for cell Pt| Q, QH,, H’ || IMKCI| He,Ch(s) | Ha()) | Pt (@) it's emf when pH = 5.0 (b) the pH when E.)=0 (©) the positive electrode when pH =7.5 given EX pis) = 0-28, E>gouss) = 0-699 ms Fora cell Mg(s)| Mg”*(aq) || Ag" (aa) | Ag, Calculate the equilibrium constant at 25°C. Also find the maximum work that can be obtained by operating the cell. E? (Mg?*/Mg) =-2.37V, BP (Ag'/Ag) =0.8V. For a cell in which the oyerall reaction is 2Cut > GP + Cu E? at 298 K is +0.184 V. Calculate AG for the raction. Is LOM. H* solution under H,S0, at 1.0 atm capable of oxidising slver metal inthe presence of 1.0 MAg* ion? Ee yg 7080, Erepyern 7O0¥ y-Electrochemistry) Find the equilibrium constant for the reaction Cu? + In ge Cut + In? Given that “hd th BP ae jqyr MOISV, BP ay a4 OAV 0 Bi} pt =~ O42 ‘The Zn?* | Zn half cell (E° = -0,762 V) is connected to a Cu?* | Cu half cell (E° = 0.34 V). What is the value of By for spontaneous conversion of chemical energy to electrical energy? ‘What is the value of log iy K, where K is the equilibrium constant? Use (2.303 RT/F) = 0,06, Ewa? Mino, = —1.51 V E°ynoyimn = + 1.23 V Bio /imo, = 7 (All in acidic medium) Calculate the maximum work that can be obtained from the Daniel cell given below - Zn) | Zn’ (aq) || Cu* (aq) | Cu (8). Given that E*,,2+ 2,=—0.76 V and E%e,2-jey=* 0.34. If for the half cell reactions Cu?! + e* —»> Cut B=0.15V Cult + 2e°—> Cu B°=034V Calculate 8? of the half cell reaction Cut +e" —> Cu also predict whether Cu’ undergoes disproportionation or not. 21. Acell contains two hydrogen electrodes. The negative electrode is in contact with a solution of 10°M hydrogen ions, The emf of the cell is 0.118 V at 25°C. Calculate the concentration of hydrogen ions at the positive electrode, EALITETTUVTERU LEU YY bi Fr i,(9) we her aamd H,80,) = 0.05M! 22, Calculate By of Pt(s) tama? |0.01M 01M given that EP, op 4 = 133V BO CrCl, =-1,36V The 2°, for the reaction Fe + Zr ==& Zn + Fe , is ~ 0.32 volt at 25°C. What will be the equilibrium concentration of Fe” , when a piece of iron is placed in a 1 M Zav* solution ? 24. MnO, (aq) + Zn(s) + H,0'(aq) > Mni*(aq) + Zn"(aq) + H,0 (1) For the above reaction if the equilibrium constant at 298 K is represented by 10%, then the value of 23, “a *< 4 4 (Given; The standard cell potential E*= 2.4 V and eet = 0.06 V at 298 K]fcuemscapes | 25. 26. 27, 28. 29. 30. 31. 32. 33. Calculate R.P, of hydrogen electrode at 298K which is prepared with the help of aq. solution of acetic acid with 0.1 M conc. at { atm pressure Ka = 1.8 x 105, Calculate K,,, if (PbSO,) E,., at 298 K of this electrode is 0.236 V Pb(s) |PbSO,(s)[Na,SO,(aq)||PO(NO,)|Pb(S) 0.01M 0.1M For a cell reaction, E (at 25°C) = 1.26V, n=2 and AS =-96.5 JK mol. Calculate E at 85°C by assuming AS to be independent of temperature. (F = 96500 C mot’) Determine Ey, for each of the following cells at 25°C. Assume activity and fugacity equal to molar concentration and pressure (bar), respectively. (i) Mg| Mgl,(0.1 mol dr) | L,(s) | Pt (E° gq) = 2:8985 V) (ii) Ag | AgBr(s) | HBr(0.02 mol dar) | H,(0.5 bar) | Pt (E°,.y =-0.0713 V) (iit) Fe | Fe(NO,), (0.05 mol dm) || Cu(NO,), (0.01 mol dm) |Cu (E° = 0-778 V) (iv) Pt| H,(g, 0.127 bar) | H'Ch | H5(g, 6.43 bar) | Pt (v) Pt| Hg (1) | HgyCl(s) | KCI(0.1 mot dv) |{ Zn2* (0.733 mol dav) | Zn (E", y= —1.10 V) The emf of the cell He | Mercurous nitrate (0.01 M) || Mercurous nitrate (0.1 M) | Hg jg found to be 0.0295 V at 25°C. Determine the molecular formula of mercurous nitrate. Calculate E® for the following reactions at 298 K (i) Ag(NH,),* + © > Ag + 2NH, (i) Ag(CN). +e > Ag +20N™ Given: E+ yp 0-7991V: K2,, (AgNH3)}) =6.02 «10° and Khas (Ag(CN)3) = 1,995 x1 Calculate the potential at 25°C for the cell Pt | H,(p = 1 bar) | HBr (a, = 0.2) | Hg,Br,(s)| He go? (Ee =0,1385 V) Br jHg2Bq lis The potential of the cell Cd | Caly(a,) | Agl(s) | Ag is 0.286 0 V at 25°C. Calculate the mean ionic activity of the ions in the solution, and the activity of electrolyte. (E°.e= 0.2508 V) The potential of the cell Za(s) | ZaC}(0.010 21 mol kg") | ABCI) | AB(S) is found to be 1.156 6 V. Waht is the mean ionic activity coefficient of ZnCl, in the solution ? (Eq = 0.984 V)34 35, 36, 3H: 38. 39. 40. 4l, 3 The emf of the cell Ag | AgCl(s) | KCl(aq) | Hg Cl,(s) | He is 0.045 5 V at 298 K and the temperature coefficient is 3.38 x 104 V K-!. What are free energy, enthalpy and entropy changes at 2908 K ? At 298 K, the emf ot he cell 0.01moldm™ KCl Imol dm™ KNO, 0.01 mol dm”? KOH sat. with HgoCl, | salt bridge | —_ sat. with HgO is found to be 0.163 4 V and the temperature coefficient of the emf to be 0.000 837 VK". Calculate the enthalpy and entropy changes of the reaction. Hg For the following cell Pb | PbCL(s) | PbCl,(soln.) | AgCK(s) | ag the potential at 298 K is 0.490 V and the variation of emf with temperature is given by E=a-—(1.86 x 104 VK") (T-25K) Caleualte AG, AH and AS for the reaction at 298 K. At 273 K, the calorimetric determination of AH for the reaction Zn(s) + 2ZAgC\(s) > ZnCl,(aq) + Ag(s) OE yielded 217.78 kJ mol, while the emf of the corresponding cell was 1.015 V. What was (=) P of the cell ? (a) At 298 K the standard free energy of formation of H,O(1) is -237.23 kJ mot", while that of its ionization to hydrogen and hydroxyl ions is 79.71 kJ mot'. What will be the reversible emf at 298 K of the cell. Pt| Hy(g, 1 bar)| H"(1 M) || OH-(1 M)|0,(g, | bar)| Pt (b) The enthalpy of formation at 298 K of H,O(1) is 285.85 kJ mol-!, while its enthalpy of ionization is 56.90 kJ mol, Calculate the temperature coefficient of the standard emf at 298 K for the cell given in part (a). Determine the standard equilibrium constant of the following reaction at 298 K. 2MnO; + 6H* +5H,C,0,+2Mn* +8H,0+10C0, (E*,,=2.0V) Determine the standard equilibrium constant of the following reaction at 298 K. Cu(OH), -> Cu? (aq) + 20H (aq) (E° eu) = 0.561 V) Given the cell Cd| Cd(OH),(s) | NaOH(0.01 mol kg!) | H,(1 bar) | Pt with E.=0.0 Vat 298K, If E¢y2+ cq =-940V. Calculate (a) K, for Cd(OH),, and (b) AG, AS of . a43. 45. 46. 47. 48. 49. 50. ale 52. 53. CHEM ACADEMY 42, es al ‘When metallic copper is shaken with a solution of a copper salt, the reaction Cu + C?* > 2Cut proceds. When equilibrium is established at 298 K, [Cu2* [Cu = 1.66 10° (mol dav). If the standard potential of the Cu2* | Cu half-cell is +0.337 V, what is the standard (reduction) potential of Cut | Cu half-cell ? Calculate the potential of the following cell at 298 K. Ca{s) | CdS0,(0.01 mo! kg", y = 0.383), PbSO,(s) | Pb— Pb| PbSO,(s), CdSO,(1.00 mol kg, 7 = 0.042) | Ca(s) Calculate the potential at 298 K of the following cell. a Zn| ZnCL,(m=0.01 mol kg", y, = 0.708) | AgCl | Ag | AgC! | hk ZnCl,(m = 0.10 mol kg, 7, = 0.502) | Zn Calculate the no. of electrons lost or gained during electrolysis of (a) 3.55 gm of Cl ions (b) 1 gmCu** ions (c) 2.7 gm of AP* ions How many faradays of electricity are involved in each of the case (a) 0.25 mole AP* is converted to Al. (b) 27.6 gm of SO, is convered to Soy Ce (c) The Cu2* in 1100 ml of 0.5 M Cu** is converted to Cu. Cr The electrosynthesis of MnO, is carried out froma solution of MnSO, in H,SO, (aq). Ifa current of Cr 25.5 ampere is used with a current efficiency of 85%, how long would it take to produce | kg of r,r Mn0,? Cr 3A current was passed through an aqueous solution ofan unknown salt of Pd for 1Hr. 2.977g of Pd* was deposited at cathode. Find n. Cr Three electrolytic cells A, B, C containing solution of ZnSO,, AgNO, and CuSO, respectively are ar connected in series, A steady current of 2 ampere was passed through them until 1.08 g of silver deposited at the cathode ofcell B. How long did the current flow? What mass of copper and of zine Cr were deposited? The conductivity of pure water ina conductivity cell with electrodes of cross sectional area 4 cm SG and 2 orn apart is 8 x 10°7S om. Ss (i) What is resistance of conductivity cell ? (ii) What current would flow through the cell under an applied potential difference of | volt ? Sa s 4 Resistance of a 0.1M KCI solution in a conductance cell is 300 ohm and specific conductance of 0.1M KClis 1.29 x 10? ohn! cnr. The resistance of 0.1M NaC! solution in the same: cell is 380 ohm. Calculate the equivalent conductance of the 0.1M NaCl solution. Sa Specific conductance of a saturated solution of AgBr is 8.486*107 ohn enr? at 25°C. Specific conductance of pure water at 25°C is 0.75 x10 ohm! cm”, A*, for KBr, AgNO, and KNO, are 1374, 133 , 131 (S om? mot) respectively. Calculate the solubility of AgBr in gnvire x Calculate the specific conductance of a 0.1 M aqueous solution of NaCl at room temperature, given that the mobilities of Na* and Cl ions at this temperature are 4.26x10* and 6.80108 nv v |, respectively.63. 65. 67. eee The EMF of the cell M |M* (0.02M) || H* (1M) H,(g) (1 atm), Pt at 25°C is 0.81V. Calculate the valency of the metal if the standard oxidation of the metal is 0.76V. The resistance of a N/10 KCI solution in 245 ohms. Calculate the specific conductance and the equivalent conductance of the solution if the electrodes in the cell are 4 cm apart and each having an area of 7.0 sq. cm. In a conductivity cell the two Platinum electrodes, each of area 10 Sq, cm, are fixed 1.5 cm apart, The cell contained 0,05 N solution of a salt. If the two electrodes are just half dipped into the solution which has a resistance of 50 ohms, find equivalent conductance of the salt solution. The equivalent conductance of 0.10 N solution of MgCl, is 97.1 mho cm? eq! at 25°C. A cell with electrodes that are 1.50 cnt in surface area and 0.50 cm apart is filled with 0.1N MgCl, solution. How much current will flow when the Potential difference between the electrodes is 5 volts ? The specific conductance ofa N/10 KCI solution at 18°C is 1.12 x 102 mho em), The resistance of the solution contained in the cell is found to be 65 ohms, Calculate the cell constant, The equivalent conductance of an infinitely dilute solution of NH,Cl is 150 and the ionic conductances of OH” and CI” ions are 198 and 76 respectively. What will be the equivalent conductance of the solution of NH,OH at infinite dilution. Ifthe equivalent conductance ofa 0.01 N solution NH,OH is 9.6, what will be its degree of dissociation 2 Given the equivalent conductance of sodium butyrate, sodium chloride and hydrogen chloride as 83, 127 and 426 mho cn’ at 25°C respectively. Calculate the equivalent conductance of butyrie acid at infinite dilution. Calculate the dissociation constant of water at 25°C from the following data : Specific conductance of H,O = 5.8 x 10-* mho cnr! 4,,, 350.0 and 2%, = 198.0 mho cm? mot! Calculate K, of acetic acid if its 0,05N solution has equivalent conductance of 7.36 mho cn? eq” at 25°C. (AZ gcoon = 390.7 mho em? mol). The sp. cond. of a saturated solution of AgC! at 25°C after subtracting the sp. conductance of conductivity of water is 2.28 x 10° mho cnr’. Find the solubility product of AgCl at 25°C. (Agece = 138.3 mho cm? mot) For H’ and Na’ the values of.” are 349.8 and 50.11. Calculate the mobilities of these ions and their velocities if they are in a cell in which the electrodes are 5 cm apart and to which a potential of 2 volts is applied. The molar conductivity of 0.1 M CH,COOH solution is 4.6 S cm? mot! , What is the specific conductivity and resistivity of the solution ? A solution containing 2.08 g of anhydrous barium chloride is 400 CC of water has a specific conductivity 0.0058 ohm-!cnr!. What are molar and equivalent conductivities of this solution. Equivalent conductance of 0.01 N Na,SO, solution is 112.4 ohm om? eq-!. The equivalent conductance at infinite dilution is 129.9 ohn! cm? eq~!. What is the degree of dissociation in 0.01 NNa,80O, solution? ' "68. 69. 70. Pl. T2 73. 75. 76. U7, 78. 79. 80. 81. | TS | he molar ionic conductivities at infinite dilution For the strong electroytes NaOH, NaCl and BaCl, t are 248.1x10-4, 126.5 x10~ and 280.0 x104 mho cm? mol respectively. Calculate the ‘molar conductivity of Ba(OH), at infinite dilution. At 25°C, 2, (H*) = 3.4982 «10-2 § m? mol"! and 2,(OH-)= 1.98 *107 $ nv'mol'. Given: Sp. conductnace = 5.1 x10-S mr for H,0, determine pH and K,. Aluminium is obtained by the electrolysis of molten Al,O, is Hall process. How many seconds would it take to obtain 120 g aluminium by a current of 9650 ampere? (Assume that the current efficiency to be 90%) Chromium metal can be plated out froman acidic solution containing CrO, according to the following equation. CrO,(aq) + 6H"(aq) + 6e" > Cr(s) + 3H,0. Calculate (i) How many grams of chromium will be plated out by 24,000 C and (ii) How long will it take to plate out 1.5 g of chromium by using 12.5 A current? (Molar mass of chromium = 52g) 0.01 M solution of KCI has a specific conductance value of 0.00141 mho cnr'. A cell filled with this solution bas a resistance of 4.2156 ohms. (a) What is the cell constant? (b) The same cell filled with a solution of HCI has a resistance of 1.0326 ohms. What is specific conductivity of the HC! solution? At 18°C the mobilities of NH,* and ClO, ions are 6.6 x 10“ and 5.7 x 10-4 cm? volt"! ¢ at infinite dilution. Calculate equivalent conductance of ammonium chlorate solution. Calculate K, of acetic acid if its 0.05 N solution has equivalent conductance of 7.36 mho cm* at = | 25°C. (Abus,coon =390.7 S cm? mol") | The resistance of an aqueous solution containing 0.624 g of CuSO, » 5H,O per 100 em? of the i solution in a conductance cell of cell constant 153.7 per metre is 520 ohms at 298 K. Calculate the . molar conductivity. (MW of CuSO, - 5H,0 = 249.5 g) | ‘An aqueous solution of 0.02 M KCI solution is filled in a 25 em long capillary tube of internal radius 0,01 em. The solution was found to have a specific conductance of 0.0027 mho em. What S will be the current in amp when a potential of 2 volts is applied across the capillary tube? e ‘A dilute solution of KCI was placed between two platinum electrodes 10 cm apart, across which a S potential of6 volts was applied. How far would the K* ion move in 2 hours at 25°C? Tonic conductance . ofK* ion at infinite dilution at 25°C is 73.52 mho em mol!, ' For 0.0128 N solution of acetic acid at 25°C, equivalent conductance of the solution is 1.4 mho cnt | eq?! and A, =391 mho cm? eq”. Calculate dissociation constant (K,) of acetic acid, The specific conductance at 25°C ofa saturated solution of AgCl in water is 1.826 x 10° mho enr!. If Aiyer is equal to 138.26 mho cm’, find out the solubility of AgCl in water in grams per litre. 5V potential is applied across 2 electrodes which are 2 cm apart. Calculate speed of the Ca** ions if | 4Ca* = 100 S cm? mol, Write answer upto 3 decimal places. 0.2 M 100 ml HClis mixed with 0.2 M 100 ml NaOH solution. If conductivity of resulting solution is found to be 0.01 Scnr!, Calculate 42 of NaCl. Given: A= 2M“; B=200 S cm? mot! M-!2, @ Give Answer in three significant figures.| | CST 1T-JAM Previous Year Questions 10. EXERCISE IV Previous Year Questions The molar conductivity of 0.009 MM aqueous solution of a weak acid (HA) is 0,005 S$ nm? mot and the limiting molar conductivity of HA is 0.03 Sm? mot! at 298 K. Assuming activity coefficients to be unity, the acid dissociation constnat (K,) of HA at this temperature is: (a) 1« 10 (b) 0.1 () 9x 104 (d) 1.1% 10% An electric current of 0.965 ampere is passed for 2000 seconds through a solution containing [Cu(CH,CN),]* and metallic copper is deposited at the cathode. The amount of Cu deposited is (a) 0.005 mol (b) 0.01 mol (c) 0.02 mol (d) 0.04 mol For the EMF of a hydrogen electrode to be zero, the pressure of hydroen required in neutral pHis: (a) 1 x 107 atm (b)1x 104 atm —(c) 1.0. atm (d) 0.0 atm The ionic strength of 0.1 M aqueous solution of Fe,(SO,), is (a) 0.1M (b) 0.65 M (c) 13M (15M Ifthe transport number of ‘Nat is 0.463 (dilute solution of NaCl in methanol), the transport number of H* (dilute solution of HCI in methanol) is (Given, q® (NaCl in methanol) = 96.9 Q-! em? mot! and 4® (HCI in methanol) = 192 1 om? mot!) (a) 0.27 (b) 0.46 (c) 0.54 (d) 0.73 The molality of (NH,))80, solution that has the same ionic strength as 1 mol kg" solution of KCL 1s (a) 13 mol kg (b) 1/2 mol kg (c) 2/5 mol kg (d) 3/5 mol kg? ‘The conductance at infinite dilution follows the order (a) Lit>Nat>K* (b) Nat>Lit>Kt ()K*>Lit> Na’ (d) Kt > Nat > Li? Use the Debye-Huckel limiting law to calculate the mean activity coefficient for the ions in an aqueous solution of potassium sulphate, K,S0,, of molality 0.010 mol kg” at 25°C. (a) 0.943 (b) 1.074 (©) 1.023 (d) 0.932 The equivalent conductance of NaCl at concentration C and at infinite dilution are do and h,, and },, is given as (where, the constant B is respectively. The correct relationship between Ae positive) ()beHhe HBC (b) 2c =%.- BNE Oh =2,-(BNE (@) de=2, +BWE Resistance of 0.2 M solutuion of an electrolyte is 50 2, The specific conductance of the solution of 0.5 M solution of same electrolyte is 1.4 S mm! and resistance of same solution of the same electrolyte +s 280 Q. The molar conductivity of 0.5 M solution of the electrolyte in ny mot? is (a) 5x 104 (b) 5x 103 (5x10 (5x10 i aaa seei. 13. 14, i. 1S eo <2 i =» fi The concentration of K* ion inside a biological cell is 20 times higher than of potential difference between the two sides is (a) OmV (b) 26 mV (¢) 77 mV (d) 177 mV An electrochemical cell consists of two half-cell reactions: AgC\(s) +e — Ag(s) + CI (aq.) outside. The magnitude Cu(s) > Cu2*(ag) + 2e~ The mass of copper (in grams) dissolved on passing 0.5 A current for 1 hour is (a) 0.88 (b) 1.18 (c) 0.29 (4) 0.59 The Zn?* | Zn half cell (E® = -0.762 V) is connected to a Cu** | Cu half cell (£9 = 340 V). What is the value of Bg for spontaneous conversion of chemical energy to electrical energy? What is the value of log,, K, where K is the equilibrium constant? Use (2.303 RI/F) = 0.06. Consider the following redox system Q+2H*+2e = QH, E°=0.699V Calculate the pH of the solution at 298 K, if the redox potential of the system is 0.817 V. Plot schematically the concentration dependence of molar conductivity of a strong electrolyte and a weak electrolyte in the same figure. The limiting ionic molar conductivities of K* and CI” are 73.5 and 76.5 S cm? mot, respectively. If the molar conductivity of 0.1 M KCI solution is 130.0 S cm? mot", calculate the Kohirusch’s constant for KCI solution. Given Eo tu a = 0,337 V and Beau) =~0.403 V at 25°C, will Cd(s) precipitate Cu(s) from a solution (assume reactants and products to be at unit activity) ? Write down the feasible cell reaction and obtain the equilibrium constant (K) for the reaction. For a cell in which the overall reaction is 2Cu* > Cu* + Cu E? at 298 K is +0.184 V. Calculate AG? for the raction. (a) The B°,,, ofan aluminiumair battery is 2.73 volts and it involves 12 electron process. Calculate the free energy change (AG*) of the battery in kJ. (b) For the following reaction H,(g) + Cch(g) = 2HCK(aq) AG? is -262 KI. Calculate the equilibrium constant (K) for the reaction at 298 K. The molar conductance of 0.012, mol dir? aqueous solution of chloroacetic acid is 100 2 cm? mot!. The ion conductance of chloroacetate and H* ions are 50 O°! om? mot! and 350. 07! em? mot", respectively. Calculate (i) degree of dissociation and pK, of chloroacetic acid, and (ii) H* ion concentration in the solution. The molar conductance at infinite dilution for BaCl,, KCl, K,S0, and CT are 260, 150, 300 and 76 Q- nf mot", respectively. Calculate the transport number of Ba”* in BaSO, solution at infinite : SCe || =| For cS 1. The standard reduction potential value: Beans = 0.17V Bong = OAaY A eee Calculate Ey... =? IIT-JEE Previous Year Questions 22, Faraday’s laws of electrolysis are related to the (b) atomic number of the anion (a) atomic number of the cation (d) speed of the cation (©) equivalent weight of the electrolyte 23. Thereaction 1/2 H,(g) + AgCl(s) > H’(aq) + Cr(aq) + Ag(s) occurs in the galvanic cell (a) Ag/AgCi(s)|KCl(soln)|AgNO,|Ag (b) PijH,(@)|HC\soln)|AgNO, (soln)|Ag (c) Pt|H,(g)|HC\(soln)|AgC\(s)|Ag (d) PU/H,(g)|KCl(soln)|Ag M(s)|Ag 24, — For the electrochemical cell, (M|M")||(X1X), E°(M*/M) = 0.44 V and E°(X/ X) = 0,33 V. From this data one can deduce that (a) M+ X— M* + X is the spontaneous reaction (bt) Mt +X°3M+X is the spontaneous reaction (0) Egy = 0-77 (4) Egy =-0-77 V 25, The correct order of equivalent conductance at infinite dilution of LiCl, NaCl and KClis (a) LiCl > NaCl > KCl (b) KCI > NaCl > LiCl (c) NaCI> KCI> LiCl (d) LiCl > KCI> NaCl 26. Inthe electrolytic cell, flow of electrons is from (a) cathode to anode in solution (b) cathode to anode through external supply (c) cathode to anode through internal supply (d) anode to cathode through internal supply 27, The half cell reactions for rusting of iron are : 2Ht +2e° + 1/2 0, > 1,00); E°=+1.23V Fe2* +26" —> Fe(), E°=-0.44V AG? (in kJ) for the reaction is (a) -16 (b) 322 (c)-122 (116 28, Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 mA current. The time required to liberate 0.01 mole of H, gas at the cathode is : (1 F=96500 C mot) (a) 9.65 * 104s (b) 19.3 « 104s (0) 28.95 x 10's — (d) 38.6 10*sCi =| | 29. 30. 31. 32: 33, AgNO, (aqueous) was added to an aqueous KCI solution gradually and the conductivity of the solution was measured. The plot of conductance (A) versus the volume of AgNO, is : (a)P @)Q ()R An aqueous solution of X is added slowly to an aqueous solution of Y as shown in column 1. The variation in conductivity of these reactions is given in column II. Match column | with column II and select the correct answer using the codes given below the columns. Column 1 Column I q Pp C Hs) Nt oe 1, Conductivity decreases and then increases a Cue IMs BEND; (0-01M) 2, Conductivity decreases and then does not change much C4 R. CH SUES KOH 3. Conductivity increases and then does not change much CF 5. NaQH+ HI 4, Conductivity does not change much and then increases Ce Codes C"F Po One ke Ss Q s (a) 3 4 2 1 (b) 4 3 2 1 OF Guess i Ie oa 2 Sh Question (31 - 33) a ‘A4,0 M aqueous solution of NaCl is prepared and 500 ml of this solution is electrolysed. This leads Sy to the evolution of chlorine gas at one of the electrodes ~ The total number of moles of chlorine gas evolved is XQ (a) 0.5 (b) 1.0 ()2.0 (93.0 Q If the cathode is a Hg electrode, the maximum weight (in gram) of amalgam formed from this Q solution is (a) 200 (b) 225 (c) 400 (d) 446 NS The total charge (coulombs) required for complete electrolysis is (a) 24125 (b) 48250 (c) 96500 (d) 193000 ‘ 34. 35. KClis increased 4-fold, the value of In y, (y, is the molar mean ionic activity coefficient) will According to the Debye-Huckel limiting law, if the concentration of a dilute aqueous solution of (a) decrease by a factor of 2 (b) increase by a factor of 2 (c) decrease by a factor of 4 (d) increase by a factor of 4 Subjective A current of 3.7 Ais padded for 6 h between nickel electrodes in 0.5 L of a 2.0 M solution of Ni(NO,),. What will be the 'be the molarity of solution at the end of electrolysis? of solution at the end of electrolysis ?