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SR IPL

ASSIGNMENT

DT:15-04-2014

SINGLE ANSWER TYPE QUESTIONS:

1.

**Which of the following best explains why concentration cells must be run under non-standard
**

conditions in order for them to do electrical work?

A) concentration cell cannot do electrical work at 25oC.

B)The change in free energy for a concentration cell is always negative under standard

conditions.

C) Concentration cell has a cell potential equal to zero under standard conditions.

D) A concentration cell can only do electrical work when either NH3 or NaOH is added

2.

Eo

for two reaction are given below :

OCl H 2O 2e Cl 2OH ; E o 0.94V

Cr 3 3e Cr ;

What will be the

E o 0.74V

Eo

for?

3OCl 2Cr 3H 2O 2Cr 3 3Cl 6OH

A) -1.68V

3.

B)1.68V

C)-0.20V

D)0.20V

**The e.m.f. of the cell
**

Cd (s) + Hg2+ (aq) Cd+2 (aq) + Hg

is given by E = 0.6708 – 1.02 × 10–4 (T – 25 V) where T is the temperature in °C and E in volts.

The entropy change for the reaction is

(A) – 19.69 J deg–1

(B) – 129.3 kJ

(C) 19.69 kJ deg–1

(D) – 9.85 J deg–1

70 V 2 MnO /MnO MnO /Mn 4 2 2 Given that under acidic conditions. The conductivity is A) Lower than that of completely ionized metal salt in water B) Higher than that of completely ionized metal salt in water C) Low than that of fused metal salt D) Equal to conductivity of liquid metal 5.09 N ) 7.4. The incorrect statement(s) among the following regarding this system is/are (I) A stable compound of the stoichiometry Mn(MnO4)2 is formed. .95 kJ 6. IV (D) II. An acidic solution of MnSO4 is mixed with KMnO4 solution.18V fumarate 2 A) -28. (A) I (B) II. E o 1. fumarate 2 i) ii) pyruvate 2H 2e lactate .03V 1 and . E20 0. E 0 0.27 kJ D) -40.59volts at 298K.47 V occurs. III. III Cd | Cd ( NO ) .23 V . IV (C) I. (IV) A redox reaction with a standard cell potential of +0.53 Kj Eo 1. From the following values of electrode potentials. (II) A precipitate of MnO2 is formed. Alkali metals dissolve in liquid NH3 and form blue coloured solution which is conductive due to ammoniated electrons.53 kJ C) -75. 2 2 H 2e succinate . EMF of the following cell is 0. (III) KMnO4 loses its pink colour. KCN || Cd ( NO ) | Cd 32 32 (0.05 N ) (2 N ) (0. Calculate G 0 for the reaction. 2 lactate succinate pyruvate B) +40.

2NKCN is equilibrium concentration.88 1019 1.88 1020 Calculate the cell EMF in mV for Pt | H 2 1atm | HCl 0.79 kJ mol–1 (B) 654 mV (C) 546 mV 9. 1.56 kJmol–1 and (A) 456 mV G f (H+ + Cl–)(aq) = 130.048 V (B) – 0.04 V (C) – 0.01M | AgCl(s) | Ag(s) Given : G f at 298 K (AgCl) = – 109. of the complex is 9 1022 (B) (A) 8. By how much would the oxidising power of the concentration is decreased 100 times? MnO 4 / Mn 2 couple change if the H+ ions (a) increases by 189 mV (b) decreases by 189 mV (c) will increase by 19 mV (d) will decrease by 19 mV The useful work done during the reaction Ag(s) + 1 2 Cl2(g) AgCl(s) Would be (a) 110kJ mol–1 (b) 220 kJ mol—1 (c) 55kJ mol–1 (d) 100 kJ mol–1 .222V Pt | H2 (1 atm) | NaOH (xM). 11. NaCl (xM) | AgCl (s) | Ag (Given ) (A) 1.6 mV Calculate the EMF of the cell at 298 K E Cl /AgCl/Ag 0. Coordination no. (C) Cd (D)279.604 V (D) emf depends on x and cannot be determined unless value of x is given 10.44 1020 is 4. The instability constant of (D) 2.

3 h then the concentration in Cu chamber is 15. Multiple Answer Type Questions: 12.E 0 D) A given lead acid storage cell posse’s constant cell potential. || Ag aq | Ag Pt. The voltaic cell using and half cells is set up at standard conditions.220V Given PCl2 1 atm and T = 298K . x 10 so value of x is : [ Given: Cu (M. |O2 P2 .E0 0 G 0. Which of the following statements are NOT TRUE? A) Use of salt bridge maximizes liquid junction potential B) For a spontaneous redox process C) For a spontaneous redox process G 0.H P |OH aq. Which of the following cell(s) can act as concentration cell? Pt.15 A for 52. The cell delivers 0.Pt 2 1 2 2 Integer Type Questions : Cu / Cu 2 Sn / Sn2 14.36V. W = 63.Pt 2 1 2 1 Pt H 2 P1 | Haq.Pt C) D) P | HCl aq. and each compartment has a volume of 240 ml.5)] The standard reduction potential for the half cell.E 0Cl 2 / Cl 1.(Give your answer as numerical) . | H P . 13.KCl aq. E 0AgCl/Ag/Cl. 0. | H P .H A) B) Ag | AgCl s . || H aq.

5 M) | AgCl (s) | Ag is 0.2422V.771V Cd | Cd2 (10. E0 Fe2+ / Fe3 0.78 V a) Calculate the reduction potential in 8M H+ b) What will be the reduction potential of the half-cell in a neutral solution? Assume all other species to be at unit concentration 16. Calculate the potential of an indicator electrode versus the standard hydrogen electrode which originally 0. Calculate a) the entropy change when 1 gm mol of silver is deposited and b) the heat of formation of AgCl. it was found that 68% of the cobalt complex was reduced to [Co(en)3] 2+ by lead. 17. Fe 3+ (Pt) [log 6 = 0.5 M) || HCl (0.HCl (0. [log 9 = 0. if the heat of formation of lead chloride is – 86000 cal. 25 mL of a solution of HCl (0.1 M NaOH solution using a hydrogen electrode as the indicator electrode and saturated calomel electrode (SCE) as the reference electrode. b) What is the maximum value of ratio for which the following will act as electrochemical cell? (Give your answer as numerical) E0 Cd / Cd2 0.6M) || Fe 2 .402V. At 25°C.1M) is being titrated potentiometrically against 0.0. i) Find the value of K for Pb + 2[Co(en)3]3+ Pb2+ + 2[Co(en)3] 2+ ii) What is the value of Eo [Co(en)3]3+|[Co(en)3] 2+ Given: Eo (Pb2+|Pb) = . the emf of the cell (Give your answer as numerical) Pb | PbCl2.(Give your answer as numerical) MnO4– + 8H+ + 5e– Mn2+ + 4H2O E° = 1.51 V [Fe2 ] [Fe ] 19.49 volts and its temperature coefficient dE 1.NO3–(aq) + 2H+(aq) + e– NO2(g) + H2O(l) is 0.8 10 4 volt / degree dT .95].1M MnO4– and 0.01 M solution of [Co(en) 3]3+.126 V(Give your answer as numerical) .778] 20.8M H+ and which has been treated with 90% of the Fe 2+ necessary to reduce all the MnO4– to Mn2+. What would be the EMF of the cell initially and after the addition of 20 mL of alkali at 25°C? Given Reduction potential of SCE = 0. [1 + 4] When a rod of metallic lead was added to a 0. (Give your answer as numerical) 18.

Ered = o Ered – 0.SOLUTIONS 1.D 9.B Mn2+ + 4H2O According to Nernst equation. B (b) MnO 4 3. A 4. D 6.059 5 E ored Ered(initial) = log [Mn 2 ] 8 [MnO 4 ][H ] [Mn 2 ] 0.A . C 10.0591 log 8 5 [MnO 4 [X] Let [H+]initial = X [H+]final = X X 2 100 10 8. 2. B + 5e– + 8H+ 5.A 7.

Hence the oxidising power decreases by 0.189 V. log PCl1/22 0 Useful work = – Wmax = – nFE = (–1) × (–1.14) × 96500 × 10–3 kJ = 110 kJ mol–1 12. 4 15.A (a)For the cell reaction Ag(s) + 1 2 Cl2(g) AgCl(s) E0 = – 1.1891 V This Ered decreases by 0.E ored Ered(final) = 0.14V or E = E0 – 0.059 [Pr oducts] log n [Re ac tan ts] The Nernst equation is E = E0 – .0591 5 log 1016 = – 0. The tendency of the half cell to get reduced is its oxidising power.0592 log PCl1/22 1 PCl2 0 Under standard conditions.189V 11.0591 [Mn 2 ] 1016 log 5 [MnO 4 ] [X]8 Ered(final) – Ered(initial) = 0. ABC 14. For the half cell reaction NO3–(aq) + 2H+(aq) + e– NO2(g) + H2O(l) 0. ABCD 13.

78 – 0.78 + 0.8 10 4 ) 4.78 – = 0.833V Substituting this value for case (b) 0.059 1 log 7 2 2 (10 ) E = 0.2 = – 4.0.14) = – 12494 cal [1] This heat of reaction is the algebraic sum of the heats of formation of the components.14 cal/degree [1] H of the reaction H = G + TS = – 11200 + 298 (–4.78 – = 0.059 1 log 2 2 (8) = 0. The net cell reaction 1 Pb Agcl(s) 2 G nFE 1 PbCl2 2 Ag 1 96500 0.059 log 8 = 0.2 = – 11260 cal S [1] d(G) dE nF dT dT = 96500 ( 1.367V 16.49 4. H HAs 1 1 HPbCl2 HPb HAgCl 2 2 12494 0 1 1 86000 0 HAgCl 2 2 HAgCl 43000 12494 = – 30506 cal/mole .059 7 = 0.

2422 + 0.3013V [1] pH after addition of 20 mL alkali: 25 0.2422 0.H (pH ?) || KCl satd.17.0591 pH at 25C [1] pH log[H ] log(0.1 HCl: Ecell = 0.5 M pH log 1.95 18. Hg(l) .5 millimole Amount of HCl initially present = Amount of NaOH added = 20 0.1 2.5 2 = 0.5 millimole 0.95 45 45 Ecell 0.08) So. Pt [1] Ecell ESCE(redn) EHydrogen(redn) = = 0.1 2 millimole Amount of HCl left unreached = [HCl = 0.1 90 8 100 (0. Pt || MnO4– (H+) | Mn+2.0591 1. 2.09) .8 0.0591 = 0.8 0 Alter Complete reaction with Fe+2 0.1) 1 Initial pH of the 0.2422 0. H2 (1atm).1 0.01) (0.1 90 100 (0.1 100 0.0591 log [ [H ] = 0.5 0. solution.: 0. electrode potential of indicator electrode Mn+2 + 4H2O 0 0.3574V [1] Let us consider Galvanic cell is H+ (1M) | H2(1atm). Pt Anode half cell : 2H+ (1M) H2 (1atm) + 2e– Cathode half cell: MnO4– + 8H+ + 5e– Initial Conc.1 0. The galvanic cell formed in this case is as follows: Pt. Hg2Cl2(s) .2422 + 0.

059 [Cd2 ][Fe2 ]2 log 2 [Fe2 ]2 [1] Here E0cell (0.395 V because ESHE = 0 19.09) log 5 (0.67 10 9 0.6[Fe2 ]2 log 2 [Fe3 ]2 [Fe2 ] 39.173V 1. E0cell Ecell 0 0.51 – (5. potential of an indicator electrode versus the SHE is 1.395 V Thus.) [Fe3 ] [Fe3 ] or.EoMnO / Mn2 EMnO / Mn2 4 4 = 0.51 – = 1.0591 (0.51 – 0.173 or.36 109) = 1.76 log0.059 [Cd2 ][Fe2 ]2 log 2 [Fe3 ]2 [1] to act as electrochemical cell.08)8 = 1.1149 = 1.6 2log[ [Fe3 ] log [1] [Fe2 ] [Fe2 ] 19. Cd(s) 2Fe3 Cd 2 2Fe2 b) The cell reaction is 0 Ecell Ecell 0.51 – 0.402) 1.059 0.01) (0. [Fe2 ] [Fe3 ] should be less than 1 1020 [1] .99log 20 (approx.0591 [Mn2 ] log 5 [MnO-4 ] [H ]8 0.0591 9 log 5 1.0591 log 5 = 1. 0.771 0.

[Co(en)3]2+ = 0..0536 V From which we can calculate E [Co(en)33+/[Co(en)32+] = 0.0068 . we get K = 0.18V . [Pb2+] = 0.303 RT log K. i) [Co(en)3]3+ = 0.0032. Ecell = -0.20.0154 ii) G10 = -nFEcell = -2. From here we get.0034 Pb Co en 2 2 1 3 3 1 3 Co en K= On putting the various known values .

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