Chemistry · Volume 2 · Chapter 9

Samacheer Class 12 Chemistry - Electro Chemistry

52 Book Back Q&AVerified AnswersFree Content

Complete Class 12 Chemistry book back solutions for Electro Chemistry with exam-ready answers.

Every answer on this page includes a verified and validated tag for study confidence.
What's on this page
Choose the correct answer 25Short answer Questions 27
Your Progress - Chapter 90% complete
Choose the correct answerChoose the correct answer25 questions
Q.1 The number of electrons that have a total charge of 9650 coulombs is: a) 6.022 × 10^22 b) 6.022 × 10^23 c) 6.022 × 10^24 d) 6.022 × 10^21

Answer: a. One Faraday = 96500 C = 1 mol e− = 6.022×10^23 electrons. 9650 C = 9650/96500 = 0.1 mol e− → number = 0.1 × 6.022×10^23 = 6.022×10^22 electrons.

Q.2 Given half-reactions: Mn2+ + 2e− → Mn(s), E° = −1.18 V and Mn3+ + e− → Mn2+, E° = −1.51 V. For the reaction 3 Mn2+ → 2 Mn3+ + Mn the E° and spontaneity of the forward reaction are:
Answer: c

Combine: reduction (cathode) Mn2+ +2e− → Mn (E° = −1.18 V) and oxidation (anode) Mn2+ → Mn3+ + e− (reverse of Mn3+ + e− → Mn2+, so E°ox = +1.51 V). E°cell = E°cathode − E°anode = (−1.18) − (−1.51) = +0.33 V. Positive → spontaneous.

Q.3 In the silver–zinc button cell (alkaline) the overall reaction is Zn + Ag2O + H2O → 2Ag + Zn2+ + 2OH−. Given half‑cell potentials: Ag2O + H2O + 2e− → 2Ag + 2OH−, E° = +0.34 V and Zn → Zn2+ + 2e−, E° = −0.76 V. The cell potential is:
Answer: c

E°cell = E°cathode − E°anode = 0.34 − (−0.76) = 1.10 V.

Q.4 The molar conductivity Λm of a 0.5 mol dm−3 solution of AgNO3 with conductivity κ = 5.76×10−3 S cm−1 at 298 K is:
Answer: b

Λm (S cm^2 mol−1) = (κ × 1000) / c(mol dm−3). So Λm = (5.76×10−3 ×1000)/0.5 = 11.52 S cm^2 mol−1.

Q.5 Given limiting molar conductances (S cm^2 mol−1) at 25 °C: KCl =149.9, KNO3 =145.0, HCl =426.2, NaOAc =91.0, NaCl =126.5. Calculate Λ°(HOAc) using appropriate values.
Answer: c

Use additivity: Λ°(HOAc) = Λ°(HCl) + Λ°(NaOAc) − Λ°(NaCl) = 426.2 + 91.0 − 126.5 = 390.7 S cm^2 mol−1.

Q.6 Faraday constant is defined as a) charge carried by 1 electron b) charge carried by one mole of electrons c) charge required to deposit one mole of substance d) charge carried by 6 22 . × electrons.
Answer: b

Faraday (F) is the charge carried by one mole of electrons (≈ 96500 C mol−1). (Option d is equivalent numerically, but definition best given by b.)

Q.7 How many faradays of electricity are required for the reduction MnO4− → Mn2+ (change in oxidation state +7 → +2)?
Answer: a

Mn changes from +7 to +2, a gain of 5 electrons per Mn; thus 5 faradays are required per mole of MnO4− reduced to Mn2+.

Q.8 A current of 3.86 A was passed for 41 min 40 s through molten CaO. The mass of Ca deposited at the cathode is (Ar(Ca)=40 g mol−1, 1F = 96500 C):
Answer: b

t = 41×60+40 = 2500 s. Q = I t = 3.86×2500 = 9650 C = 0.1 F. Ca2+ requires 2 F per mole Ca. moles Ca = Q/(2F)=0.1/2=0.05 mol. Mass = 0.05×40 = 2 g.

Q.9 During electrolysis of molten NaCl, the time required to produce 0.1 mol of Cl2 using a current of 3 A is:
Answer: b

To form 0.1 mol Cl2, electrons required = 2×0.1 = 0.2 mol e− → Q = 0.2×96500 = 19300 C. t = Q/I = 19300/3 = 6433.3 s = 107.22 min.

Q.10 The number of electrons delivered at the cathode during electrolysis by a current of 1 A in 60 s is (charge of electron = 1.6×10−19 C):
Answer: c

Q = I t = 1×60 = 60 C. Number of electrons = Q / e = 60 / (1.6×10−19) ≈ 3.75×10^20 electrons.

Q.11 Which of the following electrolytic solutions has the least specific conductance?
Answer: b

Specific conductance is proportional to concentration; the smallest concentration (0.002 N) gives the least conductance.

Q.12 While charging a lead storage battery: a) PbSO4 on cathode is reduced to Pb b) PbSO4 on anode is oxidised to PbO2 c) PbSO4 on anode is reduced to Pb d) PbSO4 on cathode is oxidised to Pb

Answer: a. During charging the negative plate (cathode) is reduced: PbSO4 + 2e− → Pb + SO4^2−. The positive plate is oxidised to PbO2. Option (a) correctly describes the cathode change.

Q.13 Among the following cells I) Leclanché cell II) Nickel–Cadmium cell III) Lead storage battery IV) Mercury cell, which are primary cells?
Answer: a

Leclanché and mercury cells are primary (non‑rechargeable); Ni–Cd and lead storage are secondary (rechargeable).

Q.14 Zinc can be coated on iron to produce galvanized iron but the reverse is not possible. The reason is:
Answer: c

Zn2+/Zn has a more negative standard potential (≈ −0.76 V) than Fe2+/Fe (≈ −0.44 V). Zinc is more easily oxidized and acts as sacrificial anode protecting iron; hence Zn coats Fe, not vice versa.

Q.15 Assertion: Pure iron when heated in dry air is converted with a layer of rust. Reason: Rust has the composition Fe2O3.
Answer: d

Correct facts: heating iron in dry air gives a black oxide layer mainly Fe3O4 (not the hydrated red‑brown rust). Rust (the flaky hydrated iron(III) oxide) is generally Fe2O3·nH2O. The assertion as stated (formation of 'rust' on heating in dry air) is not correct; the reason statement as given here (if interpreted as 'rust = Fe2O3' rather than hydrated oxide) is an oversimplification. (Given ambiguity in the printed choices, answer selected with low confidence.)

Q.16 In an H2–O2 fuel cell (alkaline medium) the reaction occurring at the cathode is: a) O2(g) + 2H2O(l) + 4e− → 4OH−(aq) b) H+(aq) + OH−(aq) → H2O(l) c) 2H2(g) + O2(g) → 2H2O(g) d) H+ + e− → H (incorrect form)

Answer: a. In alkaline fuel cells oxygen is reduced at the cathode: O2 + 2H2O + 4e− → 4OH−.

Q.17 A solution of a weak monobasic acid of concentration 3.0×10−3 M has equivalent conductance 6 S cm^2 eq−1 and at infinite dilution 400 S cm^2 eq−1. The dissociation constant Ka of the acid is approximately:
Answer: b

Degree of dissociation α = Λ/Λ∞ = 6/400 = 0.015. For a weak monobasic acid Ka ≈ cα^2 = (3.0×10−3)(0.015)^2 ≈ 6.75×10−7. Nearest option: 6.25×10−7.

Q.18 A conductivity cell is calibrated with a 0.01 M, 1:1 electrolyte whose specific conductance is κ = 1.25×10−3 S cm−1. The measured resistance was 800 Ω. The cell constant (K) is:
Answer: c

Cell constant K = κ × R = 1.25×10−3 S cm−1 × 800 Ω = 1.0 cm−1.

Q.19 Conductivity of a saturated solution of a sparingly soluble 1:1 salt AB at 298 K is κ = 1.85×10−4 S m−1. Using the molar ionic conductance at infinite dilution Λ∞ (converted consistently), calculate the solubility product Ksp = s^2 of AB (method: s = κ/Λ∞, Ksp = s^2).
Answer: d

Method: convert Λ∞ to SI units (S m^2 mol−1), find s = κ/Λ∞, then Ksp = s^2. Using typical Λ∞ ≈126.5 S cm^2 mol−1 (→0.01265 S m^2 mol−1) gives s ≈ κ/Λ∞ and Ksp ≈ (κ/Λ∞)^2 ≈ 1.7×10−6 (approximately). Selected nearest option. (Details depend on the exact Λ∞ used; answer given with low confidence.)

Q.20 In the electrochemical cell Zn | ZnSO4 (0.01 M) || CuSO4 (1.0 M) | Cu the emf is E1. If concentrations are interchanged (ZnSO4 1.0 M, CuSO4 0.01 M), the emf is E2. Which relation holds between E1 and E2?
Answer: b

Nernst: E = E° − (0.059/2) log([Zn2+]/[Cu2+]). For case 1: log(0.01/1) = −2 → E1 = E° +0.059. For case 2: log(1/0.01)=+2 → E2 = E° −0.059. Hence E1 > E2.

Q.21 Consider the change in oxidation state of bromine corresponding to different emf values as shown in the diagram. Which species undergoes disproportionation?
Answer: d

A species disproportionates when its standard potential lies between the potentials for its oxidation and reduction so it can both oxidize and reduce itself. Hypobromous acid (HOBr / HBrO) is known to disproportionate to bromide and bromate (e.g. 3HOBr → 2Br- + BrO3- + 3H+). Thus HBrO undergoes disproportionation.

Q.22 For the cell reaction with E°cell = 0.24 V at 298 K, the standard Gibbs energy ΔG° of the cell reaction is:
Answer: a

ΔG° = -nFE°. For the given cell n = 2 (two electrons transferred). Using F = 96485 C mol-1, ΔG° = -2 × 96485 × 0.24 = -46312 J mol-1 ≈ -46.312 kJ mol-1 ≈ -46.32 kJ mol-1.

Q.23 A current liberated 0.504 g of hydrogen in 2 hours. How many grams of copper can be liberated by the same current flowing for the same time through copper sulphate solution?
Answer: b

Mass H2 = 0.504 g → n(H2) = 0.504/2 = 0.252 mol. Electrons used: 2 e- per H2 → n(e-) = 0.252×2 = 0.504 mol e-. For Cu2+ + 2e- → Cu, moles Cu deposited = 0.504/2 = 0.252 mol. Mass Cu ≈ 0.252 × 63.5 ≈ 16.0 g (≈ 15.8 g given as closest choice).

Q.24 A gas X at 1 atm is bubbled through a solution containing a mixture of 1 M Y- and 1 M Z- at 25 °C. If the reduction potentials follow E°(Z) > E°(Y) > E°(X), then which is true about Y?
Answer: a

A species with a higher reduction potential will oxidize a species with lower reduction potential. Since E°(Y) > E°(X), Y (as the oxidant) can oxidize X. But E°(Z) > E°(Y), so Z will oxidize Y. Thus Y will oxidize X and not Z.

Q.25 Cell: A + 2B → A^{2+} + 2B^{+}. Given the half-reaction A^{2+} + 2e- → A has E° = +0.34 V and log K = 15.6 at 300 K for the cell, find E° for B+ + e- → B.
Answer: a

Overall reaction transfers n = 2 e-. From log K: E°cell = (2.303RT/nF)·log K. Using R=8.314 J mol-1K-1, T=300 K, F=96485 C mol-1, factor = 2.303·8.314·300/96485 ≈ 0.05956 V. So E°cell = 0.05956×15.6/2 ≈ 0.4646 V. For the cell, E°cell = E°(cathode) - E°(anode) = E°(B+/B) - E°(A2+/A). Hence E°(B+/B) = E°cell + E°(A2+/A) = 0.4646 + 0.34 ≈ 0.8046 V ≈ 0.80 V.

Short answer QuestionsShort answer Questions27 questions
Q.1Define anode and cathodev
Solution

Anode: electrode where oxidation occurs (electrons are produced). Cathode: electrode where reduction occurs (electrons are consumed). In a galvanic cell the anode is negative and the cathode is positive; in an electrolytic cell polarities are reversed.

Answer:

Anode: electrode where oxidation occurs (electrons are produced). Cathode: electrode where reduction occurs (electrons are consumed). In a galvanic cell the anode is negative and the cathode is positive; in an electrolytic cell polarities are reversed.

Q.2Why does conductivity of a solution decrease on dilution of the solution?v
Solution

Specific conductance κ depends on ionic concentration and mobility. On dilution the number of charge carriers per unit volume decreases, so κ decreases (even though molar conductivity increases due to reduced inter-ionic interactions).

Answer:

Specific conductance κ depends on ionic concentration and mobility. On dilution the number of charge carriers per unit volume decreases, so κ decreases (even though molar conductivity increases due to reduced inter-ionic interactions).

Q.3State Kohlrausch Law. How is it useful to determine the molar conductivity of weak electrolyte at infinite dilution.v
Solution

Kohlrausch's law of independent migration: at infinite dilution the molar conductivity Λm° of an electrolyte equals the sum of the ionic contributions: Λm° = ν+ λ+° + ν- λ-°, where λ±° are limiting ionic molar conductivities and ν± stoichiometric numbers. For a weak electrolyte, Λm measured at various dilutions can be extrapolated to infinite dilution, or Λm° obtained by adding λ° values of constituent ions determined from strong electrolytes; then degree of dissociation and K can be evaluated.

Answer:

Kohlrausch's law of independent migration: at infinite dilution the molar conductivity Λm° of an electrolyte equals the sum of the ionic contributions: Λm° = ν+ λ+° + ν- λ-°, where λ±° are limiting ionic molar conductivities and ν± stoichiometric numbers. For a weak electrolyte, Λm measured at various dilutions can be extrapolated to infinite dilution, or Λm° obtained by adding λ° values of constituent ions determined from strong electrolytes; then degree of dissociation and K can be evaluated.

Q.4Describe the electrolysis of molten NaCl using inert electrodesv
Solution

Molten NaCl contains Na+ and Cl-. At cathode (reduction): Na+ + e- → Na(l). At anode (oxidation): 2Cl- → Cl2(g) + 2e-. Products: liquid sodium at cathode and chlorine gas at anode. Electrodes are inert (e.g. graphite) to avoid side reactions.

Answer:

Molten NaCl contains Na+ and Cl-. At cathode (reduction): Na+ + e- → Na(l). At anode (oxidation): 2Cl- → Cl2(g) + 2e-. Products: liquid sodium at cathode and chlorine gas at anode. Electrodes are inert (e.g. graphite) to avoid side reactions.

Q.5State Faraday's Laws of electrolysisv
Solution

Faraday's first law: mass of substance liberated at an electrode is directly proportional to the total charge passed, m ∝ Q. Second law: for the same quantity of electricity, masses of substances liberated are proportional to their chemical equivalent weights. Quantitatively: m = (Q·M)/(n·F) where M = molar mass, n = electrons per formula, F = Faraday constant.

Answer:

Faraday's first law: mass of substance liberated at an electrode is directly proportional to the total charge passed, m ∝ Q. Second law: for the same quantity of electricity, masses of substances liberated are proportional to their chemical equivalent weights. Quantitatively: m = (Q·M)/(n·F) where M = molar mass, n = electrons per formula, F = Faraday constant.

Q.6Describe the construction of Daniel cell. Write the cell reaction.v
Solution

Daniel cell: two half-cells: Zn(s) | Zn2+(aq) (usually ZnSO4) and Cu(s) | Cu2+(aq) (CuSO4). Salt bridge (porous pot or KNO3 bridge) completes circuit. Anode (Zn): Zn → Zn2+ + 2e- (oxidation). Cathode (Cu): Cu2+ + 2e- → Cu (reduction). Overall: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s).

Answer:

Daniel cell: two half-cells: Zn(s) | Zn2+(aq) (usually ZnSO4) and Cu(s) | Cu2+(aq) (CuSO4). Salt bridge (porous pot or KNO3 bridge) completes circuit. Anode (Zn): Zn → Zn2+ + 2e- (oxidation). Cathode (Cu): Cu2+ + 2e- → Cu (reduction). Overall: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s).

Q.7Why is anode in galvanic cell considered to be negative and cathode positive electrode?v
Solution

In a galvanic cell oxidation at the anode releases electrons into the electrode, making it electron-rich (negative). Electrons flow through the external circuit to the cathode where reduction consumes electrons, making the cathode electron-deficient relative to anode (positive).

Answer:

In a galvanic cell oxidation at the anode releases electrons into the electrode, making it electron-rich (negative). Electrons flow through the external circuit to the cathode where reduction consumes electrons, making the cathode electron-deficient relative to anode (positive).

Q.8The conductivity of a 0.01 M solution of a 1:1 weak electrolyte at 298 K is 1.5×10^-4 S cm^-1. Find: (i) molar conductivity of the solution (ii) degree of dissociation and dissociation constant. Given λ°(cation)+λ°(anion)=248.2 S cm^2 mol^-1.v
Solution

(i) Λm = (κ×1000)/c = (1.5×10^-4 ×1000)/0.01 = 15.0 S cm^2 mol^-1. (ii) Degree of dissociation α = Λm/Λm° = 15.0/248.2 = 0.0604. Dissociation constant K = c α^2/(1−α) = 0.01×(0.0604)^2/(0.9396) ≈ 3.9×10^-5. (Values rounded to two significant figures.)

Answer:

(i) Λm = (κ×1000)/c = (1.5×10^-4 ×1000)/0.01 = 15.0 S cm^2 mol^-1. (ii) Degree of dissociation α = Λm/Λm° = 15.0/248.2 = 0.0604. Dissociation constant K = c α^2/(1−α) = 0.01×(0.0604)^2/(0.9396) ≈ 3.9×10^-5. (Values rounded to two significant figures.)

Q.9Which of 0.1 M HCl and 0.1 M KCl do you expect to have greater Λm and why?v
Solution

0.1 M HCl has greater molar conductivity. Although both are strong electrolytes at same concentration, H+ has very high ionic mobility (very large λ°) compared to K+, so Λm(HCl) > Λm(KCl).

Answer:

0.1 M HCl has greater molar conductivity. Although both are strong electrolytes at same concentration, H+ has very high ionic mobility (very large λ°) compared to K+, so Λm(HCl) > Λm(KCl).

Q.10Arrange the following solutions in the decreasing order of specific conductance: i) 0.01 M KCl ii) 0.005 M KCl iii) 0.1 M KCl iv) 0.25 M KCl v) 0.5 M KClv
Solution

Specific conductance κ generally increases with concentration (up to moderate concentrations). Decreasing order: v (0.5 M) > iv (0.25 M) > iii (0.1 M) > i (0.01 M) > ii (0.005 M).

Answer:

Specific conductance κ generally increases with concentration (up to moderate concentrations). Decreasing order: v (0.5 M) > iv (0.25 M) > iii (0.1 M) > i (0.01 M) > ii (0.005 M).

Q.11Why is AC current used instead of DC in measuring the electrolytic conductance?v
Solution

DC causes electrode polarization and electrolysis (chemical changes at electrodes) altering concentrations and producing gases. AC (usually at suitable frequency) avoids net electrochemical reaction and polarization, giving stable conductance measurements.

Answer:

DC causes electrode polarization and electrolysis (chemical changes at electrodes) altering concentrations and producing gases. AC (usually at suitable frequency) avoids net electrochemical reaction and polarization, giving stable conductance measurements.

Q.120.1 M NaCl solution is placed in two different cells having cell constant 0.5 and 0.25 cm-1 respectively. Which of the two will have greater value of specific conductance?v
Solution

Specific conductance κ is a property of the solution and is independent of the cell constant. Both cells measure the same κ (assuming ideal electrodes and identical solution and temperature); cell constant affects measured conductance G but κ = G × (cell constant) yields the same κ.

Answer:

Specific conductance κ is a property of the solution and is independent of the cell constant. Both cells measure the same κ (assuming ideal electrodes and identical solution and temperature); cell constant affects measured conductance G but κ = G × (cell constant) yields the same κ.

Q.13A current of 1.608 A is passed through 250 mL of 0.5 M CuSO4 for 50 minutes. Calculate the strength of Cu2+ after electrolysis assuming volume constant and 100% current efficiency.v
Solution

Initial moles Cu2+ = 0.250 L × 0.5 M = 0.125 mol. Charge passed Q = I·t = 1.608 A × (50 min × 60 s/min = 3000 s) = 4824 C. Moles e- = Q/F = 4824/96485 ≈ 0.0500 mol e-. Moles Cu2+ reduced = (moles e-)/2 = 0.0250 mol. Remaining Cu2+ = 0.125 − 0.025 = 0.100 mol. Concentration = 0.100 mol / 0.250 L = 0.400 M.

Answer:

Initial moles Cu2+ = 0.250 L × 0.5 M = 0.125 mol. Charge passed Q = I·t = 1.608 A × (50 min × 60 s/min = 3000 s) = 4824 C. Moles e- = Q/F = 4824/96485 ≈ 0.0500 mol e-. Moles Cu2+ reduced = (moles e-)/2 = 0.0250 mol. Remaining Cu2+ = 0.125 − 0.025 = 0.100 mol. Concentration = 0.100 mol / 0.250 L = 0.400 M.

Q.14Can Fe3+ oxidise bromide to bromine under standard conditions? Given: E°(Fe3+/Fe2+) = 0.771 V, E°(Br2/Br-) = 1.09 V.v
Solution

Consider Fe3+ + Br- → Fe2+ + 1/2 Br2. E°cell = E°(reduction at cathode) − E°(reduction at anode) = E°(Fe3+/Fe2+) − E°(Br2/Br-) = 0.771 − 1.09 = −0.319 V (negative). Thus the reaction is non-spontaneous under standard conditions. Fe3+ cannot oxidize Br- to Br2 under standard conditions.

Answer:

Consider Fe3+ + Br- → Fe2+ + 1/2 Br2. E°cell = E°(reduction at cathode) − E°(reduction at anode) = E°(Fe3+/Fe2+) − E°(Br2/Br-) = 0.771 − 1.09 = −0.319 V (negative). Thus the reaction is non-spontaneous under standard conditions. Fe3+ cannot oxidize Br- to Br2 under standard conditions.

Q.15Is it possible to store copper sulphate in an iron vessel for a long time? Given: E°(Cu2+/Cu) = 0.34 V and E°(Fe2+/Fe) = −0.44 V.v
Solution

Reaction: Cu2+ + Fe → Cu + Fe2+. E°cell = E°(Cu2+/Cu) − E°(Fe2+/Fe) = 0.34 − (−0.44) = +0.78 V (positive), so spontaneous. Fe metal will be oxidized and Cu will plate out. Therefore copper sulphate cannot be safely stored long-term in an iron vessel.

Answer:

Reaction: Cu2+ + Fe → Cu + Fe2+. E°cell = E°(Cu2+/Cu) − E°(Fe2+/Fe) = 0.34 − (−0.44) = +0.78 V (positive), so spontaneous. Fe metal will be oxidized and Cu will plate out. Therefore copper sulphate cannot be safely stored long-term in an iron vessel.

Q.16Two metals M1 and M2 have standard reduction potentials E°(M12+/M1) = -x V and E°(M22+/M2) = +y V respectively. Which metal will liberate H2 from dilute H2SO4?v
Solution

A metal will displace hydrogen from acid if it is more easily oxidised than H (i.e. its reduction potential is more negative than 0.00 V). Since E°(M1) = -x V < 0, M1 is more reactive than H and will oxidise to M1n+ releasing H2. M2 with positive E° is less reactive than H and will not liberate H2 from H2SO4.

Answer:

M1 (the metal with negative reduction potential) will liberate H2 from dilute H2SO4; M2 (with positive E°) will not.

Q.17Given E°(Fe2+/Fe) = -0.44 V. Two metals M1 and M2 have standard reduction potentials E°(M1) and E°(M2). Which metal is better for coating (electroplating) iron?v
Solution

For electroplating onto iron the coating metal must be reduced preferentially on Fe (not allow Fe to oxidise). That requires E°(coating metal) > E°(Fe2+/Fe). Therefore whichever of M1 or M2 has E° > −0.44 V will plate on iron and serve as a coating. (If E°(M) < −0.44 V, iron will be oxidised instead and coating won't form.)

Answer:

The metal whose E° is more positive than −0.44 V (i.e. more noble than Fe) is better for coating iron.

Q.18Calculate the standard emf of the cell Cd(s)|Cd2+||Cu2+|Cu(s) and determine the cell reaction. Given E°(Cu2+/Cu) = +0.34 V and E°(Cd2+/Cd) = −0.40 V. Predict feasibility.v
Solution

Cell notation: Cd(s)|Cd2+||Cu2+|Cu(s). Cathode is the half-cell with higher (more positive) E°: Cu2+/Cu (0.34 V). Anode: Cd2+/Cd (−0.40 V). E°cell = E°cathode − E°anode = 0.34 − (−0.40) = 0.74 V. Oxidation at anode: Cd → Cd2+ + 2e−. Reduction at cathode: Cu2+ + 2e− → Cu. Net: Cd(s) + Cu2+ → Cd2+ + Cu(s). Since E°cell > 0, the reaction is spontaneous.

Answer:

E°cell = 0.74 V. Cell reaction: Cd(s) + Cu2+ → Cd2+ + Cu(s). Reaction is spontaneous (feasible).

Q.19In a H2–O2 fuel cell H2 is oxidised at the anode and O2 reduced at the cathode. If 44.8 L of H2 at 25°C and 1 atm reacts in 10 minutes, what is the average current produced? If the entire current is used to electroplate Cu from Cu2+, how many grams of Cu are deposited? (M(Cu) = 63.55 g mol−1.)v
Solution

Molar volume at 25°C ≈ 24.45 L mol−1. Moles H2 = 44.8 / 24.45 = 1.832 mol. Each mole H2 → 2 e−, so total charge Q = n( H2) × 2F = 1.832 × 2 × 96485 = 3.536×10^5 C. Time = 10 min = 600 s. Current I = Q/t = 3.536×10^5 / 600 ≈ 589 A. For Cu2+ + 2e− → Cu, moles Cu deposited = moles H2 (since 2 e− per H2 and 2 e− per Cu) = 1.832 mol. Mass = 1.832 × 63.55 ≈ 116.5 g.

Answer:

Average current ≈ 589 A. Mass of Cu deposited ≈ 116.5 g.

Q.20The same amount of electricity was passed through two electrolytic cells containing Ni(NO3)2 and Cr(NO3)3. If 2.935 g of Ni was deposited (M(Ni) = 58.74 g mol−1), how many grams of Cr were deposited? (M(Cr) = 52.0 g mol−1.)v
Solution

Moles Ni deposited = 2.935 / 58.74 = 0.05000 mol. Ni2+ + 2e− → Ni so electrons used = 0.05000 × 2 = 0.10000 mol e−. Same total electrons deposit Cr3+ via Cr3+ + 3e− → Cr, so moles Cr = 0.10000 / 3 = 0.033333 mol. Mass Cr = 0.033333 × 52.0 = 1.733 g.

Answer:

Mass of Cr deposited = 1.733 g (approx).

Q.21A copper electrode is immersed in 0.10 M CuSO4 at 25°C. Calculate the electrode potential of the copper electrode. (E°(Cu2+/Cu) = +0.34 V.)v
Solution

Nernst equation for Cu2+ + 2e− → Cu: E = E° + (0.0591/2) log[Cu2+]. Substitute: E = 0.34 + (0.0591/2) log(0.10) = 0.34 + 0.02955 × (−1) = 0.340 − 0.02955 = 0.31045 V ≈ 0.310 V.

Answer:

E = 0.310 V (approximately).

Q.22For the cell Mg(s)|Mg2+(aq)||Ag+(aq)|Ag(s), calculate the equilibrium constant at 25°C and the maximum (non-expansion) work obtainable. Given E°(Mg2+/Mg) = −2.37 V and E°(Ag+/Ag) = +0.80 V.v
Solution

E°cell = E°(cathode) − E°(anode) = 0.80 − (−2.37) = 3.17 V. Net reaction: Mg + 2Ag+ → Mg2+ + 2Ag, so n = 2. At 25°C, E° = (0.0591/n) log K ⇒ log K = nE°/0.0591 = 2×3.17/0.0591 ≈ 107.3 ⇒ K ≈ 10^107.3 (extremely large, reaction essentially complete). Maximum electrical work per mole reaction: w_max = −nFE° = −2 × 96485 C mol−1 × 3.17 V ≈ −6.11×10^5 J mol−1.

Answer:

E°cell = 3.17 V. Equilibrium constant K ≈ 10^107.3 (very large). Maximum work w_max = −nFE° ≈ −6.11×10^5 J per mole of reaction (n=2).

Q.23A lake contains 9.2×10^12 litres of water. A reactor electrolyses the lake water at a steady rate delivering a charge at I = 2.0×10^6 C s−1. How many years would it take to completely electrolyse the water? (Assume no losses; 1 L water = 1000 g; M(H2O)=18 g mol−1.)v
Solution

Moles of water = (9.2×10^12 L) × (1000 g L−1) / 18 g mol−1 = 9.2×10^15 / 18 ≈ 5.111×10^14 mol. Electrolysis: 2 H2O → 2 H2 + O2 requires 4 e− per 2 H2O ⇒ 2 e− per H2O. Charge needed Q = (moles H2O) × 2F = 5.111×10^14 × 2 × 96485 ≈ 9.87×10^19 C. At I = 2.0×10^6 C s−1, time t = Q/I = 9.87×10^19 / 2.0×10^6 = 4.935×10^13 s = 4.935×10^13 / (3.1536×10^7 s yr−1) ≈ 1.57×10^6 years. Note: numeric result depends on the assumed current; replace I if different.

Answer:

Approximately 1.6×10^6 years (about 1.57 million years) under the stated assumption I = 2.0×10^6 C s−1.

Q.24Derive the Nernst equation.v
Solution

Start from thermodynamics: ΔG = ΔG° + RT ln Q. For an electrochemical cell, ΔG = −nFE and ΔG° = −nFE°. Substitute: −nFE = −nFE° + RT ln Q ⇒ divide by −nF ⇒ E = E° − (RT/nF) ln Q. Converting ln to log10 and inserting numerical constant at 298.15 K gives E = E° − (2.303RT/nF) log10 Q = E° − (0.05916/n) log10 Q (≈0.0591/n at 25°C).

Answer:

E = E° − (RT/nF) ln Q (general form); at 25°C E = E° − (0.0591/n) log10 Q.

Q.25Write a note on sacrificial protection.v
Solution

In sacrificial (cathodic) protection a metal with a more negative electrode potential (e.g. Zn, Mg, or Al) is electrically connected to iron or steel. The active metal serves as the anode and corrodes (is 'sacrificed'), while the iron becomes the cathode and is protected from oxidation. Applications: galvanising (Zn coating on iron), sacrificial anodes on ships, underground pipelines and storage tanks. Advantages: simple and effective; requires periodic replacement of sacrificial anode.

Answer:

Sacrificial protection uses a more active metal (anodic) attached to iron/steel so the active metal corrodes preferentially and protects the iron.

Q.26Explain the function of H2–O2 fuel cell.v
Solution

Typical proton-exchange membrane (PEM) fuel cell reactions: Anode: H2 → 2H+ + 2e−. Cathode: 1/2 O2 + 2H+ + 2e− → H2O. Net: H2 + 1/2 O2 → H2O; E°cell ≈ 1.23 V (standard). Electrons flow through the external circuit producing current; protons migrate through the membrane. Catalysts (Pt) enhance kinetics. Products are electricity and water; fuel cells have high efficiency and low pollution (no CO2 if H2 is from non-carbon source).

Answer:

H2–O2 fuel cell converts chemical energy of H2 + 1/2 O2 → H2O into electrical energy via separate oxidation (anode) and reduction (cathode) half-reactions with an external circuit.

Q.27Ionic conductances at infinite dilution of Al3+ and SO42− are 189 and 160 mho·cm2·equiv−1 respectively. Calculate the equivalent and molar conductance at infinite dilution of the electrolyte Al2(SO4)3.v
Solution

For Al2(SO4)3: ν(Al3+) = 2, ν(SO42−) = 3. Ionic conductances are given per equivalent. Molar ionic conductance = z × (ionic conductance per equiv). For Al3+: z = 3 ⇒ contribution = 2 × 3 × 189 = 1134 mho·cm2·mol−1. For SO42−: z = 2 ⇒ contribution = 3 × 2 × 160 = 960 mho·cm2·mol−1. Molar conductance Λ°m = 1134 + 960 = 2094 mho·cm2·mol−1. Number of equivalents per mole of Al2(SO4)3 = total positive charge = 2×3 = 6. Hence Λ°eq = Λ°m / 6 = 2094 / 6 = 349 mho·cm2·equiv−1.

Answer:

Equivalent conductance Λ°eq = 349 mho·cm2·equiv−1. Molar conductance Λ°m = 2094 mho·cm2·mol−1.