ELECTROCHEMISTRY (ADVANCE DAY-1 (Types of electrolytic cells-Galvanic cells, Electrolytic cells) | 1 Which of the following is/are function(s) of salt - bridge? (A) It completes the electrical circuit with electrons flowing from one electrode to the other through external wires and a flow of ions between the two compartments through salt — bridge (8) It minimizes the liquid — liquid junction potential (C) Both correct (D) None of these 2. Which one of the following statements is incorrect regarding an electrochemical cell? (A) The electrode on which oxidation takes place is called anode. (8) Anode is a negative pole (C) The direction of current is same as that of flow of electrons (O) The flow of current is partly due to flow of electrons and partly due to flow of ions. 3) Which one of the following statements is wrong about an electrochemical cell (ECC) and an electrolytic cell (ELC)? (A) ECC produces electricity, ELC consumes not (8) Anode of ECC is negative while anode of ELC is positive (C) Anode of ECC is negative while anode of ELC is positive (0) In both ECC and ELC, the redox reaction is spontaneous. 4. Which is/are true about the salt bridge? (A) Any salt can be employed to construct the bridge (6) Only salts containing cation and anion having equal ionic mobilities can be employed (C) During the operation of cell, anions of the salt rush into the anodic half cell and cations into the cathodic half cell to maintain the electrical neutrality of the two solutions (0) Salt bridge gives rise to liquid-liquid junction potential (Mechanism of electrolysis - products at electrodes) | 1. solution of sodium sulphate in water is electrolysed using platinum electrodes. The products at cathode and anode are respectively. (A)H,,0; (B)O,,H, (C)O,,Na (D) 0,80, 2. Which one is the wrong statement about electrochemical series? (A)Active metals have negative reduction potential (B)Active non-metals have positive reduction potential (C) Metals above hydrogen liberate hydrogen from acids. (D) Metals below hydrogen are strong reducing agents, IEE Hyderabad Contors Saifabad ¢ Narayanaguda Dilsukhnagar—# —Kukatpally‘SP-WB(VIN(A)-CH(EC)-2 3. Onelectrolysis, which of the following will not given out oxygen? (A) Acidic water using Pt electrode (B) Fused NaOH using Pt electrode (C) Dilute H,SO, using Pt electrodes (D) Dilute H,SO, using Cu electrode 4. Addilute aqueous solution of Na,SO, is electrolyzed using platinum electrode. The products at the anode and cathode are: (A) Oa, He (B) S,03", Na (C) Oz, Na (0) 8,03, DAY-3 (Faraday’s laws of electrolysis) passed through an aqueous solution of NaCl for a time of 1.0 hr. How 1 A constant current of 30 A is duced? What is volume of Cly gas at S.T.P. produced? many grams of NaOH are pro a mercuty cathode. How long trolysis of a solution of CdCl using odin 0 valgam on a cathode of 2g. H Cd amalgam is prepared by ele’ Seid a current of 5A be passed in order to prepare 12% Cd-Hg am (Atomic weight of Cd = 112.4)3. SP-WBIVIN(A)-CH(EC) 3 3A current metal was passed through an aqueous solution of an unknown salt of Pd for 1Hr. 2.9779 of Pd" was deposited at cathode. Find n. (Given Atomic mass of Pd = 106.4) How long a current of 3 amp has to be passed through a solution of AgNOs to coat a metal surface of area 80 cm? with a thickness of 0.005 mm? Density of Ag is 10.5g cm™. Three electrolytic cells A, B, C containing solution of ZnSQ,, AgNO; and CuSO. respectively are connected in series. A steady current of 1.5 ampere was passed through them until 1.45 g of silver deposited at the cathode of cell B. How long did the current flow? ‘What mass of copper and of zinc were deposited?| SP-WB(VI(A}-CHIEC)-4 6. A solution of silver nitrate was electrolysed using silver electrodes, each weighing 20g. & ‘one ampere was passed for 10 minute. Find the weights of electrodes after ‘ecueen tite 7. Accurrent of 2.6 amp is passed through 25 ml, 0.8 N Fe,(SO.); solution for 3 minutes with # cureni efficiency of 95%. Find out the molarity of ferric ion after the deposition of iron. Assume no volume change. Iculate pH of solution 8 A current of 0.193 amp is passed through 100 m! of 0.2M NaCl for an hour. Cal after electrolysis if current efficiency is 90%. Assume no volume change10. SP-ANELVINYA}-CHIEC)S les through 100m! of a 0.1M NaC! solution, the cathode reaction taking place is 2e" + 2H;0 ——» H2(g) + 20H" ‘At the anode, Ch is liberated, Using this information, calculate the pH of the final solution after electrolysis. A current of 0.1 ampere is passed for 16 minute ‘Ammonium persulphate is prepared by the anodic oxidation of ammonium hydrogen ‘sulphate to the reaction: NH,HSO, ——> NHSO, +H” 2NH,SO, —> (NH4)2S:0s + 2¢'... 2H* #2e° ——> Hp......-..-.. cathode: H,02 can be prepared by the hydrolytic reaction (NH,)zS205 + 2H2O ——> 2NHsHSO, + H2Oz ‘Assuming 60% current efficiency in the production of persulphate, calculate the amount of current necessary to produce 170gms of H,Oz. Yield in hydrolytic reaction is 80%. anode ‘Pata Vyderabed Corte eeRicnencene 20) Mnatmatly — & Mivanur‘SP-WBIVIN(A)-CH(EC)-6 HCE TICE "1 12. is in series using inert On passing 0.5 mole of electrons through CuSOx and Haz (NOs)z solutions i 9 electrodes: deposited (A) 0.5 mol of Cu deposited eos = Ld peed (C) 0.125 mol of ©, produced (0) 0.5 me ining FeSOx, Fez (SO,)s, If same quantity of electricity is passed through three electrolytic cells containing 4 Fez (SO,)s, andFe(NO3),, then ual (A) The amounts of iron deposited in FeSO, and Fez (SOx), are ea! ee i ted in (8) The amount of iron deposited in FeSO, is 1.5 times of the amount of iron deposi (NOs), (C) The amounts of iron deposited in Fe, (SO,)3 and Fe(NO3), are equal (0) The same amount of gas is evolved in all three cases at the anode. 13, DAY-4 (EMF, SHE, electrochemical series, | Assertion (A): When 2 faraday of electricity is passed through 0.1 M HzSO,(aq), 11.2 litre O2 evolved at STP. Reason (R): Molecular weight of oxygen is 32. (A) Both A and R are true and R is the correct explanation of A. (B) Both A and R are true but R is not correct explanation of A (C) Ais true but R is false (0) Ais false but R is true "AC notation of cells) Determine the potential of the Daniel cell, initial (I) ion and 4.00 M zinc (II Ee lan™ = 0.76 V. Ee aigSP-WBIVIIIKA}-CHIEC}T The emf of the cell Ag|Agl|KI(0.05M)| AgNO, (0.05M)Ag is 0.788 V. Calculate the solubility product of Agl. ECVE EE = 2 How much will the reduction potential of a hydrogen electrode change when its solution intially at pH = Dis neutralized to pH = 7? (A) Increase by 0.059V (B) Decrease by 0.059V(C) Increase by 0.41V (0) Decrease by 0.41V Given Eng =0-80V, Eire jyg =-297 Vs Ee sey = O.94V Ergring = O-78V Which of the following statements is/are correct (A) AgNOs can be stored in copper vessel (C) CuCé, can be stored in silver vessel (B) Cu(NO,), can be stored in magnesium vessel (0) HgCl, can be stored in copper vessel in the electrochemical series in decreasing electropositive character is The position of some metals ‘Cu > Ag. What will happen if a copper spoon is used to stir a solution of given below: Mg > Al > Zn > aluminium nitrate? (A) The spoon will get coated with aluminium (B) An alloy of copper and aluminium is formed (C) The solution becomes blue. (D) There is no reaction. ‘A solution is one molar in each of NaCl, CdCh, ZnCh and PCI. To this tin metal is added. Which of the following is true? Given: =-0.763V, Boi =—O.12Z6V, Eby, =—0-196V, Eon icy = 0.40. Eee ics = EE igg = -2TIV (A) Sn can reduce Na* to Na (B) Sn can reduce Zn? (C) Sn can reduce Cd** to Cd () Sn can reduce Pb™ to Pb. WaTIE4 Hyderabad Centers Seifabed 6 Narayanaguda —¢ Dilsukhnagar 6! Kukatpally ¢ | Miyapur, promarme: ° ‘pwomanert2 pmowanrerie pumas: prroataneastanSP-WBCVINAY-CH(EC)S ‘The reaction Cu"? (aq) + 2CI(aq) > Cu(s) + Ch(g) has E2,y = -1.02V. This reaction 7. (A) Can be made to produce electricity in a voltaic cell (6) Can be made to occur in an electrolytic cell (C) Occurs whenever Cu’ and CI are brought together in aqueous solution (D) Can occur in acidic solution but not in basic solution 8. The EMF of a concentration cell consisting of two zinc electrodes, one dipping into SOL. of zine M sulphate & the other into 760 of the same salt at 25°C is (A) 0.0125 V (8) 0.0250 v (©)0.0178v (0) 0.0356 V DAY-5 (EMF, SHE, electrochemical series, Free energy-driving force, Nernst equation) 1-4. Forthe cell: 2+ Iougt znf?Pea||C4%a\cy Given: | =+0.35V hm {lam ett ice 0 = ES an jaq =~ OTE 1. Write cell reaction E° Cell Calculate the value for xSP-WBIVIINA)-CHIEC)9 3. Calculate the value for E cai 4. The minimum concentration of Cu* at which cell reaction is spontaneous if Zn” is 1M, 5. Show that E°,.3/p_12 = SE eastice~ E re2/re Soe + emma ESR «a, + are pS seeSP-WBCVINKA)-CH(EC)-10 6. The voltage of the following celll is 0.987 V Pt (Hz) (1 atm) | HOCN (1.4% 10-° M) |] Ag*(0.8M) | Ag(s) 0 Calculate Ky of HOCN, EQ... = 0.80 V 7. For the reaction 4 Al(s) + 302(g) + 6H,0 + 40H” —> 4 [AI(OH).I Ren = 2.73 V if AGP [OH] = -157 kJ / mol AGP [H20 ]= — 237.2 kJ / mol Determine AG? [Al (OH).J°, (free energy of formation of [AKOH).J” For the cell Mg(s) | Mg** (aq) || Ag"(aq) | Ag(s), Calculate the equilibrium constant at 25°C and the maximum work that can be obtained during operation of cell. Given Eine 2.37 V and ENO IAG =+0.80V,R=8.314JSPAWBIVINAY-CHIEC) 14 Two electrochemical cells are assembled in which the following reactions occur: ve + VO + 2H? —+ 2v" +H,0 E Sey = 0.616 V y+ Ag’ +H,O ——> VO" +2H"+Ag(s) E25, = 0.439 V Calculate E° for half reaction V"* + ev" Given E°Ag’/ Ag = 0.799V EB or re iS Xz then what will be Ez, ire to. Epis 1S Xr 11. Consider the standard reduction potentials (in volts) as shown in Fig. Find ey soy 2, soy 28". 8,0 of (ITEC Hyderabad Centers: Saifabad <6 Naravananuda — @ Milenkthnanar Abs Kasbatnnte += =~» SP.WBCVINYA)-CHEC)-12 12, From the following information, calculate the overall stability constant Ks of 3 [AaS203)] at 25°C Ag’ +e Ag E°=0.799v 13, 14. 7 [A9(8:05),]° +0--+ Ag+ 28,032; ers .017 volt The standard potential of the following cell is 0.23 eV at 15°C and 0.21 V at 35°C. PtlH2(g) | HCl(aq) | AgCl(s) | Ag(s) (i). Write the cell reaction. LW) Calculate 4H° and AS° for the cell reaction by assuming that these quantities remain unchanged in the range 15°C to 35°C Ail} Calculate the solubiity of AgCI in water 25°C. Given: The standard reduction Potential of the Ag’ (aqy/Ag(s) couple is 0.80 V at 25°C. Given E° wn7"ne2* and E° od Hun2+ are 1.51 V and 1.23 y, Calculate Ee. 7 Me at. 2g of different half celis are given below 15. red gi eect ore Oa pou 7 O84Vs 852 pzq = OTE, fe tag” 0.80V, on mp7 23 Inwhich cell is AG? most negative (A) Zn | Zn™ (1M) || Mg** (1M) | Mg (B) Zn | Zn** (1M) || Ag’ (1M) | Ag (C) Cu] Cu" (1M) || Ag* (1M) Ag (D) Ag | Ag’ (1M) || Mg" (1M) | Mg 16. For the cell Zn(s) | Zn**||Cu"*|Cu(s), the standard cell voltage is 1.10 V. When a cell using these reagents was prepared in the lab, the measured cell voltage was 0.98 V. One possible explanation for the observed voltage is (A) There were 2.00 mole of Zn** but only 1.00 mole of Cu** (B) The Zn electrode had twice the surface of the Cu electrode (C) The [2n**] was larger than the [Cu*) (0) The volume of Zn® solution was larger than the volume of the Cu” solution 17. 100 mi of a buffer of 1M NH(aq) and 1M NH," (aq) are placed in two voltaic cells separately. A current of 1.5 A is passed through both the cells for 20 minute. If electrolysis of water only takes place, 2H,O +02 + 4e7- —+ 40H” (RHS) 2H,0 —» 4H" + O; + 4e" (LHS) then pH of (A) LHS half cell will increase (8) RHS half cell will increase (C) Both half cells will increase (0) Both half cells will decrease 18. The cell Pt(H,)(1atm)|H" (pH=)||r (a=1)|Agl(s),Ag has emf, Ensex=0. The standard electrode potential for the reaction Ag! +e" -> Ag +I” is -0.151 volt. Calculate the pH value. (A)3.37 (B)5.26 (C)2.56 (0) 4.62 19. MnO, +8H* +5e° —>Mn* +4H,O IH’ concentration is decreases by 0.38 V with decrease in oxidizing power (A) The potential decreases by 0.38 V with decrease in oxidizing power (B) The potential increases by 0.38 V with increase in oxidizing power (C) The potential decreases by 0.25 v with decrease in oxidizing power (0) the potential decreases by 0.38 V without affecting oxidizing power 20. At equimolar concentrations of Fe’* and Fe®, what must [Ag’] be so that the voltage of the galvanic cell made from the (Ag" | Ag) and (Fe** |Fe*’) electrodes equals zero? Fe* + Ag’ ——=Fe™ +Ag Eang = 0-799 Ee rpyee =0.771 (A) 0.34 (8) 0.44 (c)0.47 (0) 0.61 The equilibrium constant for the reaction Sr(s) + Mg"*(aq) == Sr'*(aq) + Mg(s) is 2.69 x 10” at 25°C. The E° for a cell made up of the Sr/Sr'? and Mg"iMig half cells. (a) 0.3667V (8) 0.7346v (©) 0.1836V (0) 0.1349 ated ryderbad Carte Saifsbad ¢ Narayanaguda Dilsukh . ' oom? Neraperageds ¢ ec’ * Ruatpally,¢ ieee a‘SPANBIVINYA)-CH(EC)-14 UT CORRECTORUONT RE 22. Which of the following changes will cause the free energy of the cell reaction to decrease? Zn|2nSOg(oq) («iM HHCI.9) (aM Hag Pt (A) Increase in the volume of HCI solution from 100 ml to 200 ml (8) Increase in pressure of hydrogen from 1 atm to 2 atm (C) Increase in molarity x2 from 0.1 to 1M (D) Decrease in molarity x, from 1M to 0.1 M 23. _ In order to obtain more useful work from the electrochemical cell: Zr4q) fen (1 om)cue:, (i onc cone should: (A) increase both [ze] and [Cu** ] to 2.0M (8) decrease [zn?*] to0.1m (C) increase [ou] to2.0M (D) reduce both [zn] [out] 10 0.1M The concentration of potassium ion inside a biological cell is at least twenty times higher than the outside. The resulting potential difference across the cell is important in several process such as transmission of nerves impulses and maintaining the ion balance. A ‘simple model for such a concentration cell involving a metal M is: M(s)|Ms, (0.05M)||M;, (1M)|M(s) For the above electrolytic cell the magnitude of the cell potential is |E,. 24. For the above cell, (A) E.4 <0;AG > 0. (B) Eg >0;AG <0 (C) Ex, <0;AG° >0 (0) E,4, > 0:6? <9 25. If the 0.05 M solution of M* is replaced by a 0.0025 M solution potential would be: (A) 35 mV (8) 70 mv (©) 140 mv Of M’, then the magnitude of the cell (0) 700 mvSP-WBIVIII)(A)-CH(EC)-16 DAY- 6 (Some special half cells- metal/metal insoluble salt electrodes) 1 Calculate the EMF of the following cell Pt(Ha, tatm) | CHsCOOH (0.15M) || (0.01 M) NH,OH | He, Pt (tatm) K, for CgHsCOOH = 1.4 x 10°; Ky for NH,OH = 1.8 x 10° When a rod of metallic lead was added to a 0.01M solution of [Co (en) ]", it was found that 68% of the cobalt complex was reduced to [Co(en),)*" by lead i) Find the value of K for Pb + 2{Co (en)3)*" ——= Pb” + 2[Colen):]** ii) What is the value of E® [Co (en)s)* | [Co(en):}* Given: E° (Pb** | Pb) = - 0.126 V 3. Calculate the cell potential of a cell having reaction: AgzS + 2e” -» 2Ag + S* in a solution buffered at BH = 3 and whichis also saturated with 0.1 M H,S. For H2S: Ky = 10 and Kz = 1.1 x 10°", Kyp(AgaS) = 2 x 107°, E°(Ag’/Ag) = 0.8 ‘ANTE Hyderabad Contore ‘Ssifabad__¢ Narayanaguda ¢Dilsukhnagar—¢> ‘Kukatoally = #Mivaouree ‘SP-WBYVIIXA}-CH(EC}16 Cak 6. Iculate Eo ing? from the following thermodynamic data: 4 2 «keh mor Ma(s) + % Ox(9) = MgO(s) eo 1 = 572.9 MgO(s) + H,0(1) = Ma(OH)a(s) Seis H,0(I) = H2(s) + % O2(s) +2413 Bard auto protolysis constant Ky for water at 298°K =, 1.00 x 10". Iubilty product of Ma(OH), at 298°K = 5.50 x 10°" 5. The cell Pt, He (1 atm) |H” (pH =»)! Normal calomel Electrode has EMF of 0.67 V at 25°C Calculate the pH of the solution. The ‘oxidation potential of the calomel electrode on hydrogen scale is 0.28 V. = 10°) and 1.0 M in NaA is placed in two latinum electrodes are inserted jin each ‘Assuming electrolysis of water only at difference in pH of the cathodic lire buffer solution which is 1.0 M HA (Ke 6. on partments (0.5 lire in each) of an electrolytic cell. The pl comPstment andt.O A Curent s passed fot 128.67 mute. arent or and gnring te volume change, any, caewate cach comp erurons afer passage of he above charge waned ¢ 1 MerponagutaSP-WEIVINALCHEC)17 7. The EMF of cell ‘Ag | AgCl, 0.05M KCI || 0.05M AgNOs | Ag is 0.788 Volt Find the solubility product of AgCl. 2 For the galvanic cell AglAgClis), KCI (0.2M) || KBr (0.001M), AgBr(s) [Ag : Calculate the EMF generated and assign correct polarity to each electrode for a spontaneous process after taking an account of cell reaction at 25°C. Given Kp (AgCl) = 2.8 x 10° , Ksp (AgBr) = 3.3 x 10” 9. The solubility product of silver iodide is 8.3 x10" and the standard potential (reduction) of Ag, Ag” electrode is +0.800 volts at 25°C . The standard potential of Ag, AgI/I" electrode (Reduction) from these data is (A)-030V (8) +0.15V (©) +0.10V (0)-0.15V ‘PHUIEC Hyderabad Centers‘SP-WB{VIIIA)-CH(EC)-18 DAY-7 (Reversible electrodes, Concentration cells-types) —_—_—_—_——— 1, Cale Soe = : Of the cell, Zn—Hg(oM)|2n?* (aq|Hg—Zn(c,M) at 25°C. if the of the zinc amalgam are: c; = 10g per 100 g mercuty and cp = 1g per 100g of mercury, 1e voltage of cell at 298 K Which of the following expression(s) represent th 2. Agys)|_ Ag! |jAg2C20. 8 est | °° ‘a i Ag Ag (AE cat cela (8) Econ = 0.0592 i “| [*0'], "|, 3 2K sp (Ag2C20, (Chan 0.050209 ASEH) (©) Ee 005021091 0 (A820204) | _ Kop (Adl) [ep (Aal)] a Consider the cell: Agi.) |AgCI(saturated solution)| [A9NOs(aq)(1 om Ags) (Kep of AgC!= 1.0% 10" tw?) 1 [Kop (Aact)] EMF of the above cell is given by 12 (A)Eceu = E20 +0,0592109[Ksp (A9C!)] (B) Ecgy = 0.0592109 (C)Ecen = 0.0592 5V (D) Ecen = 296mVSP-WBIVIN)(A}-CH(EC)-19 DAY-8 (Reversible electrodes, Concentration cells-types) 4 Determine the degree of hydrolysis and hydrolysis constant of aniline hydrochloride in M/32 solution salt at 298 K from the following cell data at 298 K. Pt | Hp (1 atm) | H® (1M) || M/32 CyoHsNH-HCI (aq) | Ha (1 atm) | Pt, Ecos = -0.188V. 2. Given the cell : Cd | Cd(OH)a(s) | NaOH (0.01 mol kg") | H2(1 atm) | Pt With Ezai= 0.0 V at 298 K. If E942 gq =— 0-40 V, Calculate Ks for Cd(OH)z Calculate EMF of the following cell ‘Ag(s) | AgaCrO, (Sat. solution)|| KBr (0.002M), AgBr (s) | Ag(s) Given Ksp (Ag2CrO,) = 4 x 10°” and that of AgBr is 2 x 10"SPNBIVEKAL-CHIEC) 20 Zinc granules are added in excess to 750 mi of 1.5 M Ni (! ‘Solution siboched EME ot ake 2c " HCN) Hag) eae = ) (1 atm), Pris 0.24 calculate the amount of Zn consumed. (Zn = 65). ad pause at 30°C until the equilibrium, 0.76 vot and that of cell Ni INC} at equilibrium. Also fing Calculate the equilibrium constant for the reaction Fe? +Ce™ =—Fe™ + Ce™ Given: Ex for Pt, Hg) (190 mm Hg) | H” (10”” M) || Ce"* (0.2M) | Ce"%(1M), Ptis 1.794 V Ee ice2 OM. Esp, O.04V For the colt INH,Cl (0.01 M) + NH.OH (0.2M) | He (1\atm) | Pt PUL He (1 am | CHa = 1.8 x 10°. Inthe anode neglect TH from oxidation of Hp. Heo aay e 18x 10". Calculate the cell potential —_—-r ST ipa Contr Saifabad + Narayanaguda » ¢ DilgukhnagarSP ELYYA)-CHIECY 21 | 2 ‘The emf of the following Daniel cell Zn/ZnSO,(0.0%)|| CuSO, (1.0M)| Cu at 296K isE,. When the concentration of ZnSO, is changed to 1M and that of CuSO, to 0.01M, the emf changed to, What is the relationship between E,&E, ? (AEP Er (8) Ey Pb(s) + S04?(aq), E° = 0.34 y Calculate Ecau of the spontaneous reaction at 298k, given [soz] = 2.0M, pH = 1 and othe, species are at unit concentration. of 40% by weight (density 1.256 gm / ml) to one of 30% by weight. The original volume of electrolyte is 1.2 litre. How many faradays have left the anode of the battery. Note that water is produced by the cell reaction as H2SO, is used up. Overall reaction is PD(s) + PbO, + 2H»SO, (I) —> 2PbSO,(s) + 2H,0 o Ives the use of 25% of the Ph ; the electrode reaction invol f 8nd PbO, available init for te reaction, What shoud be te mun mas ead nh "92 2nd combined Staten so ; prey pe meray change f raacian? Aterage vollag® of lead storage battery is 2.0 V. ao : raSP-WBIVIIA)-CH(EC}-23 4 A uel cell uses CH, (g) and forms CO?> at the anode. It is used to power a car with 80 Amp. For 0.96hr. How many litres of CH, (g)(STP) would be required? (V,, =22.4L/ mol) (F = 96500). Assume 100% efficiency. CEe 5. The thermodynamic efficiency of fuel cell is given by nFE -nFE (B) —— (C) (D) nFE®. (A) AH/ AG (8) AG (Cc) aH (0) DAY-10 (Conductance) ee ee ee! SUBJECTIVE = 80Q~'om*mol". Calculate the value of 1 Gwen: "(3° 630~cm’mor" and »® (380% 1° (Alp(804);) ‘ried Hedarabad Cantars“sp-wocvniyAar-cHtECh24 _ ee is 109. The ion cond f a 0.014 N solution of chloroacetic acid is 109. The ion conduct 2 The equivalent conttrogen ions are 40.2 & 349.8 respectively, Carirare * of chlor Hoge ree of dissociatic 2) iseosaton content of acid tance 3 The equivalent conductivity of 0.05 N solution of a monobasic acid is 15.8 S cm? eq”. if equivalent Dr ontity of the acid at infinite dilution is 350 S em? eq" (@) Degree of dissociation of acid (b) Dissociation constant of acid The resistance of a solution ‘A’ is 50 ohm and that of solution ‘B’ is 100 ohy ab i taken in the same conductivity cell. If equal volumes of solutions Aand Bare mixed, Writtions bei fesistance of the mixture using the same cell? (Assume that there is ng increase in i Will be the dissociation of A and B on mixing). © degree of‘SP-WBIVIIA)-CH(ECH25 5, The increase in the molar conductivity of HC! with dilution is due to (A) Increase in the self ionization of water (8) Hydrolysis of HCI (C) Decrease in the self ionization of water —_(D) Decrease in the interionic forces. 6 Equivalent conductance of saturated BaSO, is 400 hm” cm? equiv” and specific Conductance is8x10-Sohm“cm™t. Hence Kyy of BaSO, is (A) 4x 10° M* (B) 1x 10M? (C)2x 107M (D) 1x 10M? 1. The ionization constant of a weak electrolyte is 25x10" while the equivalent conductance of its 0.01 M solution is 19.6 S cm* eq’. The equivalent conductance of the electrolyte at infinite dilution (in S cm? eq") will be (A) 250 (B) 196 (C) 392 (D) 384 8 Which of the following curve represents the variation of hy with JC for AgNOs? \ a || nq \ thee, (A) - (8) cet (c) - (0) Ba 9. Molar conductance of BaCf,,H,SO, and HCE at infinite dilutions are x,,x, and x, respectively. Equivalent conductance of BaSO, at infinite dilution will be: X, +X) —X5 XX =X wl 1 el ) a +%-24) 2 2 10, Assertion (A): Molar conductivity increases with decreases in concentration for weak electrolytes Reason (R): No. of ions per unit volume decreased due to dilution. (A) Both A and R are true and R is the correct explanation of A (8) Both A and R are true but R is not correct explanation of A (C) Ais true but Ris false (0) Ais false but Ris true TATIe€ Hyderabad Centers Saifabad ' ¢ Narayanaguda © Dileukhnagar = Kukatpally Miyapur Prcouo-crrveat prc om-eeaate2 Pr usecase prccuocaessat Pac OAbMMBSP-WB(VIIIYA)-CH(EC)-26 DAY-1 1 (Special topics like corrosion, conductometric titrations) 4. The equivalent conductivity of 0.10N soluti ion of MgCh is 9 ? eg K Lis 97.18 + at 25% electrodes that ae 1.50 cm i Gurtac area and O50 om apt ised win ON Mg ci Slaton How al tow when the potential difference between tne elecvodes i 5 VON? een 2. A sample of water from a large swimming pool has a resistance of 9200 ohm at 25°C when placed in A satin conductance cell. When filed with 0.02 M KC ‘olution the cell has a resistance of 85 ohm at 25°C. 500 grams of sodium ‘chloride were dissolved in the pool which was thoroughly stirred. A Sample of this solution gave a resistance of G00 ohm. Calculate the volume of water in the Poot » Given molar conductivity ‘of sodium chloride at that concentration is 126.5 ohm ‘¢m?mor' and molar conductivity of potassium chloride at 0.02 M is 138.3 ohm ‘em?mot '‘SP-WBIVIIXA)-CH(EC}-27 3, Ammetal is left exposed to the atmosphere for some time. It gets coated with green carbonate. The metal must be (A) Silver (8) copper (C) ron (0) Zine. 4. Which graph best represents the electrical conductivity behavior that occurs when an aqueous solution of acetic acid, CHsCOOH, is titrated with an aqueous solution of sodium hydroxide, NaOH? | “ ' @) | a I (©) i (0) 5. Which of the following graphs will correctly correlate E.o as @ function of concentrations for the cell (for different M and M)? Zn(s) + Cu’*(M) — Zn"2(M) + Cu(s), E0.9= 1.10V (2n"?} (cu?) X-axis: log Y-axis: Ect 4.10 4.10 ry (B) «) ay (0) 400 +10 6. Which one of the following statements is incorrect? (A) Specific conductivity decreases with dilution (B) Equivalent and molar conductivities increase with dilution (C) A,, for a weak electrolyte cannot be found by extrapolation of the graph between A and Concentration to zero concentration. (0) Molar conductivity of a strong electrolyte increases with dilution because ionization increases with dilution. ‘ROE Hyderabad Cotors ‘Saliabad 6 Narayanaguda —¢Digukhnager 6 Kukatpally + Miyapur a Sr ower peumats —° premauansos aeSPAVBIVIN(A)-CH(EC)-28 % The variation of A, of acetic acid with concentration is correctly represented by w * @ a © 7 () 2‘SP-WB(VIN(A)-CH{EC)-28 ANSWERS ELECTROCHEMISTRY (ADVANCE 5 c 2c Direction of conventional current is opposite to that of flow of electrons. haa) In ECC only, redox reaction is spontaneous. 4 BC DAY-2 1A 2 oD 3. 7D “4 A DAY-3 1.12 mol, 12.535 litre. 1=93.65 sec n 125.1 sec moles of Ag deposited = 10.5x 80x 0.005 0. 1 108 since 1F of charge deposits teq equivalents of Ag deposited = 3.88x 10> (n factor = 1) Charge in coloumbs = 3.88x 10" x 96500 = 3.8810"? x 96500 3 Sens = 3.88x10% t =125.1sec 1.45 €9(A) deposited = Fog = 0013 = ne. of faradays 0.013 x 96500 = 1.5xt 36.34 sec, €9(AB) 495 = @a(Cu) =eq(Zn) -. wt(Cu) = 0.013 x ss 835 _ 9.4129 wi(Zn) = 0.013 x 33 -o.424g 19.328g and 20.671 g x10%60 eq(Ag),,, = 10x80 (9) cop =~ 96500 Jae, = 1080 ep ~ “96500 wa(ac Rx? 5-108 = 0.6719 ILE Hyderabad Centers Saifabad Narayanaguda¢ Dilsukhnagar* ~Kukatpally Miyapur‘SP-WB(VIN)(A)-CH(EC)-30 10. weights of electrodes after electrolysis = 20-0671 = 19.3289 and 20 + 0.671 = 20.6719. 0.236M 2.6x3x60x95 Faradays of charge used = 46x10 ceria eh 96500100 <. Moles of Fe"? ions = 2x3.33x10 3 n(Fe**) deposited = 46x10 _0.76x10> Molarity of Fe”? (6.66%10°9 -0.76x10°*)» "2 =0.206M. PH = 12.81 2NaCl + 2H,0 —22—>H, + Cl, +2NaOH 96500 C > 1 mole (NaOH) 0.193 3600 . 90 3 », n(NaOH) = —————— x —— = 6.48 x1 n(NaOH) = S50 48x10 [ow ]- $48x10" oe 6.48x107 » PH = 12.81 PH = 12. 2NaCl + 2H,0 —22> H, + Ck +2NaOH _ 0.1% 16x 60 Faradays of charge = —~c5555 4 —— forms 1 mole (NaOH) 0.1x16%60 3 4 = OE = 9.9x10™ = = n(NaOH) = “96500%0.1 558.43 ampere. {NH),8,0¢, (NH),S:0s + Hs0 -> 2NHHSO4 + H2Oz 2289 3g «94 g H20r is produced by 228 g (NHs), S205 : 228 “170 g H,02 will be produced by =,-%1709(NH,), $,0g:0 =11409 Equivalent mass of (NHa):SzOx may be calculated using the fol 2NH4SOq — (NH4 )2 Se Equivalent mass of (NH4)2S20; Molmass 228 2 Satta Og +20 lowing reaction :SP-WBIVINKAY-CHIEC)-34 From first law of electrolysis, oe 36500 1%3600«114 1425 = Seep = 338.08 Given that, current efficiency is 60%, the actual amount of current = 558.43 ampere. 11. B,C 12. B,Cc,D 13. B DAY- 4 ON 1 Ex11V Initiaty [Cu’? ] =[2n°?] = foeyeadee ee 0 C= ¥ 96500 2 sEeN 2x 1g (Cu"?) formed n(cu*?) 4 5.48 x10°% -3 2 104 548x109 (20), ed ” 96500 "2 |eu'?|=1+5.18%10- [zn°2|=1-5.18x10°° now the cell functions as galvanic cell ~. the reaction is Cu’? + Zn > Zn"? + Cu 0.0591, 1-5.18x10°° lo. 2 145.18x10° a14 E=1.1V Kep =1.16x10-* D c D Cu is less reactive than Al. D Check the spontaneity of each reaction by finding the E.M.F. B cSP-WB(VINYA)-CH(EC)-32 DAY-5 SS Zn + Cu"? 5 Zn? + Cu 1. 2. Egy = [40.38 ~ (-0.76)]=1 a a =1.11V 3. Econ = 1.1189V [z*'] 0.059, 4 1.11- > cu] 7 -1189V = 1.114 2952..0.3010 4 [cw?] 5.9x10°°M. “3 - ¥ = ; 5. Fe+3e>Fe Cre ners 42 - : Pe, Fe’? + 2e° > Fe Freire ae resi 3 te ee fi Se. Fe +e >Fe’ Eee Fe? ie G9 = aG? - AG? =F = -3FE? -(-2FE2) 0 +26? 260 . 0 -[3€6,9160 ~ 26° .¢9] Fe’? /Fe 6. 36x10 0.987 = (0.8-0) — (H*)=5.5x10* 55x14 nth +OCN 14x10 Aare =04 a 4.410°3 (1- a)5.5%10 2 Ke 14x10 (04) _ 36x10 0-04)1". 12. (1) 2) Mn’? + 36° > Mn“* eg =? ‘SP-WB(VINA)-CH{EC)-33 GP [A(OH), | = 1303kImoI-* For given cell reaction, = 12x 2.73 x 96500 J = -3.1613 x 10° kd 7 Aae > APY +120 308 +12e > 607 Now for given reaction, ace = 4x GP[AI(OH), 6x6? ([H,0]-4xG9 [OH] (Also note that GP for elements is zero ) = 3.1613 x 10° = 4x cP [AN(oH), | -6x(-237.2)-4x(-157) = GP [AI(OH), | = 1303kImor" 864 x10" = 611.8k) oe logkag 0.8 -(-2.37) = Keq = 2.864 1017 -AG? = Wimax Wmax = +NFE® = 2x96500%3.17 =611.8kJ 0.059 2 Econ = logkeq -0.256V 3x, — 2x, -0.756V Ks = 5.86 x 10" Ag> Ag’ +e E°=-0.799V co e [Aa(S20s), | me 0+ 28209" _ 60 _got7y —gP = 2.059199 [Aa(S20s), | Ag" +282037 7 Ks = 5.86 x 10" Hy +2Agt 2H? +2Ag £8 =1.69V Mn‘7+5e Mn? = -(1) E2 =1.51v Mn'*+2e°->Mn‘? = -(2) E9 =1.23V AGS = AG? - ac? ~3FEQ = (-5Fx 1.51) -(-2xFx1.23) 8 =1.69V ‘ANUEE Hyderabad Centers @ Nerayanaguda ¢ Dilsukhnager @—sKukatpally ¢ = Miyapur‘SP-WB(VIIIN(A)-CH(EC)-34 15. 20. 24. 25. DAY: 1 D A ee 1 1 io | a 0A 22 CD 23, B.C B The gi i given cell is not electrolytic cell; it is electrochemical (concentration cell) cell Als AG > 0 or AG <0 is wrong. It should be AG = +ve or AG = -ve. |E.a.|=70mV means may be + ve or - ve Now, Eos = Eons + Ena 0.059 ~ 2258 jogh] +E + 2S Io0[M Ia . [Mm] 0.059lo, las - 0,059l0g—= oh am .059|09- oe 059 x1.30 = 0.076 V =76mV ~70MV E,4, = +ve and AG =—ve it is. electrochemical (concentration cell) cel Also c The given cell is not electrolytic cell AG =+ve or AG=-ve. AG > 0 or AG <0 is wrong. It should be [E cal =70mV means may be +ve or ~ Ve Now, Feet = Borne + ERP as £2, 225% o9[a],, Ee +5 POL uw [8 Tue cose! > HS =0.059l0g 5 55 =0.089I00F FT hs =0.059x1.30 =0.076V =76mV ~70mV 1 1 - __1__ 9.05909 Ey = 0.0591095 9995 °9 (0.08) = 2x76 =152~140 Note: See the difference in E,_) values. -0.0318¥. Ecol = fy 0 OEE [Je cal 2A aso, (arate) a (19-39% x00) = 0.0315. rn saitabed_¢ Narayanaguda + "Disukhnagar —¢ _Kukatpally «Miya nna + Miyapur‘SP-WB(VINY(A)-CH(EC)-25 2(c y° (cof (en), )” 26° —+2[c0(en), i? Pb —, Je re ee 2 Ks [Co(en), 5. PO) —2[coen),|"? spr? Saul: 32x 10° gg 4q-9 88x10 2 (oantos} een: So: (a2e103 F =1.5x10 0 .Ke 0 0.0591, () Elen = Hog 13.6x10°8 0 Eco cor ~ 0.126 = -0.053 =0.072V ) 101.110 0.1 [orf fo 0 0.0591 rent Free loa Ky = 0.8 =" og2x 104 Learn - =-0.639V «=, for the reaction AgyS +2e" + 2Ag+s* Es -0.639-2 FP higgt. 4x10" 0.167 V Mg +40, =MgO -572.9 MgO +H,0 = Mg(OH),, 31.2 HO =H, +402 4241.3 Mg+2H,O =Mg(OH), +H, AG°=~362.8 AG: 2.303RTlogk -362.8%10° 8.314 «2,303 x298 k = 3,84 x10 k= Antiog 2H* +20H” = 2H,0 10° 7 12 Mg(OH), = Mgt? + 20H 5.5x10 aaa ae am Meg + Kula, +, Myspue saiabag + Maryanagute 9 Diguager at, 6 MYSP-WB(VIN)(A)-CH(EC)-36. —eooS4$44S Mg +2H* = Mg?* +H, = 24.12% 1983+28-12 Kag = 21.1210! = 21.12<10°79 0.059 0.059 79 = log21.12% 107? = 2.37 2 kag 7092 Feet = En *Eagiagtt > Egg =2:37 5 pH=6.61 6. 2.295 7. Ksp = 1.16 x 10°" 0.788 = 0. 20584 (Ag*) = 2.32% 10-15 (cr) = 0.05 (given) ~ Ksp = 1.16 x 107° & = ~0.037V Thus, to get Exa positive, polarity of cells should be reversed, te. Cellis Ag | AgBr(s) KBr | AgCI, KCI | Ag and E = + 0.097 V 0.001 M 02M Nowfor LHS Kyp, =2.8x10-10 . [-a"][or] 2.8x19-10 2.810" 2.81010 “ery 02 for R.H.S Kspayq, = 3:3%1079 [49° J[er-]- +] - 33x10" _ 3.310719 [»"]- Br 0.001 =1.4x10°M 3x 19-13 =3.3x10-10y 0.059 10 BYEG (1) Bean = > logys 3:3 10"10 1.4x102 =~0.037 Thus, to get Ex positive, polarity of cals g ie., Cellis Ag TAQBI(S) KBr || AQCI, Ke | noon ae eversed, 0.001 M 02M Es +0037)NN" DD DONDE IT oS ag 8 ‘SP-WB(VILIYA)-CH(EC)-37 A 02 4x 10° 0.188 = 970.0591,,) 4 (+) cathode je = 659x104 CgHsNH3 +H20——CeHsNH, +H30* a(-2) = = but 6.59x104 = = 0.02 _ 1132(a) ~ (Fa) Ky = 1.4% 10° 2 1.626 x 10°" Cd > Cd + 267 EO ae ica =-0.4V tae" 2H 22H, Epeltiie, =O Cd+2H* ca’? ae 04 = Bey = A Pho St » (ca?) =3.4310" = Ksp = 48° = 1.626 x 107" 0.0591, 104 3 Egy = 0- SPN og ay = 0.9546V 113 12 [A] _ {4x10 a . JAg,CrO,, 4 13, 4 (ao"), = AO =o Egy = 0 oSMNigg 10 = o.a546v AgBr 2x10? : aea ‘SP.WBIVIN(A)-CH(EC)-38 17 (aq) = 4.236% 10 1125x Milimoles of Zn consumed = 1125 Weight of Zn = “a8 = 73.1259 Eyer = “0-24 1125-x x At equilibrium 24 0.059 [20 ] 0.059 0.24 = jog —_J . 0.76 - 0.2 2 TN?) 0.52 = 2 TogK (aq) Kaq) = 4:236x 10"7 x _ - 4,236x10"7 a 1125-x x 1017 x2 M25x4.296 x10" _ 4495 4.23610" So, all the [Ni] is converted to Ni Milimoles of Zn consumed = 1125 Weight of Zn = “ess 3.1259 k=1.941x1097 . 3(-0.04) +2(0.44) E563 pe? 7 =~0.76V Era +2 oe x12 ey = 1.44 Fe’? Ce" = Fe'? +Cer? Fo" Fo? 2.2 =-22_ _ 37.288 '09k = 5 059 k =1.941%1097 Eve = 0.2625 V : = [Kw 1 109 ors 107 [OH Joona “5 fie = Yat 8109 #75 2. (H')= 1.3.x 10 e 6[02) 36.404 [OH py 18210 [33] 36 591, 1.3108 Feat =F 93 6.107 Eat ® 0.2625 y i. 8 . 11.40DAY-9 oe ‘SP-WB(VIIIYA)-CH(EC)-38 Econ = 1.191 V PbOz,) + 4H" + SOZ? + 26° -> PbSOg,) +20 =E°=1.7V Pb(s) + Oz? (aq) —> PbSOy,) +2e7 EP=+0.3 1V PDO 245) +Pb(_) +2804? + 4H’ —> 2PbSO4(s) E044 = 2.01V Eg 22. 01-295 iog [1] 2P Ea = 1.191 V 27.91 = no. of faradays used. Before electrolysis : wtof solution = 1200x 1.256 = 1507.29 40 4 = 1507.2x = - wt of HzSO, 1507.2 x =oy = 602.88 9 wt of HO 1507.2-602.88 = 904.32 g After electrolysis x MO\emey = M(H2SO4) used 7p 798 = wUH2SO,) used 98x Wt (H2SOu)en = 602.88 -—~ weight of solution = 1507.29 + x 5x98 % wt of final solution 98x 602.88 - x 1507.2+x-% x98 x= 502.49 n(H20), = 602.88 — 5.44 x = 452.16 + 0.3x 5.44 x 502.4 Normed ~ 4g = 27.91 = no. of faradays used. AG°=-nFe° *96500*2=-386kd Re... in the lead storage battery. Pb + PbO, + 2H,SO, -> 2PSO, + 2H;0 Here 2 moles of electrons will exchange 1 mole of Pb or PbO2 or 100% usage generates 2F couloumbs :. Charge in coloumbs to be generated =no, of faradays used = 503604 ined = 1:865F _ 1.865 TesD = 1865F «no, of moles of Pb required = ~—==— =“ (for 100% usage) for 25% usage, we need 1.865 0 =nFE® 1865 , 100 3 73moles oe ar =2%96500*2=-386kJ 8 c Thermodynamic efficiency of fuel cell = -nFE/ AH . TAITE€ Hyderabad Centers Saifabed ¢ Narayanaguda# Dilaukhnagar—#° Kukatpally MiyapurDAY-10 1 858Scm? mor" an(ar's) =3x63Scm?mol* An (SO: x80 Scm’mol ++ AyAlp (SOg), = 2x 169 + 3 x 80 x 2 = 858Scm? mol’ a) 0.28 b)1.254 x10* a) 4° = 40.2+4349.8 = 390 109 Foy = 0:28 390 Co? _ 0.014x(0.28)? ia 1-0.28 158 = 45x10? 369 45x10 2 (0) Ke= C,? = 0.08(4.5%10)' = 1.01104 = 1.524109 1 luti tky=—xl For solution A: ky =F 1 For solution B : ky = ——xx ‘or sol 2 = 799 1 1 For mi S(ky+kp)=3xx lixture: al 4 +k2) 2 R= 66.670hm D 6. D 7. c A‘SP-WBIVIIYA}-CHIEC)-41 K _ 971x109 = 0.0295 0. 9.71 x 10° scm K=Cx K_ 9.7110 Ks 2.011% 10°L For NaCl solution: = Kx1000 _ 196.5 Ce = 0.0295 Here the 1st objective is to determine k (specific conductance) of NaCI and then C(NaC!) -«(4 i kx1000 C ki os HK = 000 Now from equation (ji), K (cell constant) = KR = 2.766 x10 x85 = 0.235cm™* Now, conductance of water. Ee = OH = 305 2.766 x10°Q"om™* 1 Conductance of NaCl aq) = Cnackaa) = 7600 = Conductance due to NaCl alone = a - = = 22.88x108 a4 = k(NaCl) = CK = 22.88% 10-0" x0.235cm™ Substituting in equation (i) 6 1265-5: i x1000 38x10 Ftc = C(NaCl) = 4.25«10-°M Number of moles of NaCl _ 500 => Volume of swimming pool = ee 1 Ps Molarity 58.5% 4,25x10> =2.011%108Lrrr ‘SP-WB(VIIIXA)-CH(EC)-42 2B CuCOs is green, ac a) 6. o me inetease in molar conductivity of any strong electrolyte with dilution is due to decrease in the intetionic forces. oc