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Chemistry · Class 12 Science

Ch 2Electrochemistry — Class 12 Chemistry, concept-first.

Objectives After studying this chapter, you should be able to: - describe what an electrochemical cell is, and tell a galvanic cell apart from an electrolytic cell; - apply the Nernst equation to find the emf of a galvanic cell away from standard concentrations, and define the standard potential of a cell; - relate a c…

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Key concepts

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Chapter contents

The NCERT structure, section by section. Open a section to see its questions, then read the concept-first solution.

Introduction

Objectives After studying this chapter, you should be able to: - describe what an electrochemical cell is, and tell a galvanic cell apart from an electrolytic cell; - apply the Nernst equation to find…

2.1

Electrochemical Cells

A redox reaction always has an oxidation half and a reduction half, and if those two halves are forced to happen in separate compartments — connected only by a wire and a salt bridge — the electron tr…

2.2

Galvanic Cells

A galvanic cell is an electrochemical cell that converts the chemical energy of a spontaneous redox reaction directly into electrical energy.

2.2.1

Measurement of Electrode Potential

The potential of an individual half-cell, by itself, cannot be measured. Only the difference between two half-cell potentials can be measured — and that difference is exactly the emf of the cell they…

2.3

Nernst Equation

Every standard electrode potential listed in Table 2.1 is measured with all species at unit concentration (1 M for ions in solution, 1 bar for gases) and 298 K.

2.3.1

Equilibrium Constant from Nernst Equation

Consider the Daniell cell with its circuit closed, driving the reaction

2.3.2

Electrochemical Cell and Gibbs Energy of the Reaction

4 Q

The electrical work obtainable from a cell in one second equals the potential multiplied by the charge that flows.

2.4

Conductance of Electrolytic Solutions

Before we can talk about how well an electrolyte solution conducts electricity, we need a few terms carried over from the physics of resistance.

2.4.1

Measurement of the Conductivity of Ionic Solutions

An unknown resistance can ordinarily be measured very accurately on a Wheatstone bridge. Trying to use this directly on an ionic solution, however, runs into two difficulties:

2.4.2

Variation of Conductivity and Molar Conductivity with Concentration

7 Q

Both conductivity and molar conductivity change as the concentration of an electrolyte changes. Conductivity always decreases with dilution, for weak and strong electrolytes alike — this is simply bec…

2.5

Electrolytic Cells and Electrolysis

A galvanic cell lets a spontaneous redox reaction generate electricity on its own. An electrolytic cell works the other way round: an external DC source is connected across two electrodes, and the ele…

2.5.1

Products of Electrolysis

What actually comes out at the two electrodes during electrolysis depends on two things: the nature of the material being electrolysed, and the type of electrode used.

2.6

Batteries

A battery is a practical, everyday source of electrical energy built from one or more galvanic cells joined in series.

2.6.1

Primary Batteries

In a primary battery, the cell reaction occurs only once — after the reactants are used up over time, the battery is dead and cannot be revived.

2.6.2

Secondary Batteries

A secondary battery differs from a primary one in that it can be recharged: once discharged, passing a current back through the cell in the reverse direction restores the original reactants, so the ba…

2.7

Fuel Cells

Ordinary thermal power plants are not a very efficient way to generate electricity, and they pollute heavily.

2.8

Corrosion

Corrosion is the slow, spontaneous eating away of a metal's surface by the formation of oxides or other salts of that metal.

The Hydrogen Economy

Fossil fuels like coal, oil, and gas power most of the world today, but burning them releases carbon dioxide, which traps heat and drives climate change — melting polar ice, raising sea levels, and th…

Summary

- Electrochemical cells convert chemical energy to electrical (galvanic) or vice versa (electrolytic).

Exercises

+Show 18 questions18 questions
  1. 2.1Arrange the following metals in the order in which they displace each other from the solution of their salts: Al, Cu, Fe, Mg and Zn.Free
  2. 2.2Given the standard electrode potentials: $K^+/K = -2.93\ V$, $Ag^+/Ag = 0.80\ V$, $Hg^{2+}/Hg = 0.79\ V$, $Mg^{2+}/Mg = -2.37\ V$, $Cr^{3+}/…Free
  3. 2.3Depict the galvanic cell in which the reaction $Zn(s) + 2Ag^+(aq) \rightarrow Zn^{2+}(aq) + 2Ag(s)$ takes place. Further show: (i) Which of…Free
  4. 2.4Calculate the standard cell potentials of galvanic cell in which the following reactions take place: (i) $2Cr(s) + 3Cd^{2+}(aq) \rightarrow…Preview
  5. 2.5Write the Nernst equation and emf of the following cells at 298 K: (i) $Mg(s)|Mg^{2+}(0.001\ M)||Cu^{2+}(0.0001\ M)|Cu(s)$ (ii) $Fe(s)|Fe^{2…Preview
  6. 2.6In the button cells widely used in watches and other devices the following reaction takes place: $Zn(s) + Ag_2O(s) + H_2O(l) \rightarrow Zn^…Preview
  7. 2.7Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their variation with concentration.Preview
  8. 2.8The conductivity of $0.20\ M$ solution of KCl at 298 K is $0.0248\ S\ cm^{-1}$. Calculate its molar conductivity.Preview
  9. 2.9The resistance of a conductivity cell containing $0.001\ M$ KCl solution at 298 K is $1500\ \Omega$. What is the cell constant if conductivi…Preview
  10. 2.10The conductivity of sodium chloride at 298 K has been determined at different concentrations and the results are given below: | Concentratio…Preview
  11. 2.11Conductivity of $0.00241\ M$ acetic acid is $7.896 \times 10^{-5}\ S\ cm^{-1}$. Calculate its molar conductivity. If $\Lambda^0_m$ for aceti…Preview
  12. 2.12How much charge is required for the following reductions: (i) 1 mol of $Al^{3+}$ to $Al$? (ii) 1 mol of $Cu^{2+}$ to $Cu$? (iii) 1 mol of $M…Preview
  13. 2.13How much electricity in terms of Faraday is required to produce (i) 20.0 g of Ca from molten $CaCl_2$? (ii) 40.0 g of Al from molten $Al_2O_…Preview
  14. 2.14How much electricity is required in coulomb for the oxidation of (i) 1 mol of $H_2O$ to $O_2$? (ii) 1 mol of $FeO$ to $Fe_2O_3$?Preview
  15. 2.15A solution of $Ni(NO_3)_2$ is electrolysed between platinum electrodes using a current of 5 amperes for 20 minutes. What mass of Ni is depos…Preview
  16. 2.16Three electrolytic cells A, B, C containing solutions of $ZnSO_4$, $AgNO_3$ and $CuSO_4$, respectively are connected in series. A steady cur…Preview
  17. 2.17Using the standard electrode potentials given in Table 3.1, predict if the reaction between the following is feasible: (i) $Fe^{3+}(aq)$ and…Preview
  18. 2.18Predict the products of electrolysis in each of the following: (i) An aqueous solution of $AgNO_3$ with silver electrodes. (ii) An aqueous s…Preview

Answers to Intext Questions

These are the final answers printed at the end of the NCERT chapter. The book gives answers for some intext questions only — every question below links to our complete worked solution.

Exemplar Problems

Higher-order thinking / exemplar-style practice problems.

+Show 68 questions68 questions
  1. Q1Which cell will measure standard electrode potential of copper electrode? (i) $Pt(s) \mid H_2(g, 0.1\ \text{bar}) \mid H^+(aq., 1\ M) \paral…Free
  2. Q2The electrode potential of a magnesium electrode varies with the concentration of Mg2+ ions according to $E_{Mg^{2+}\mid Mg} = E^{\circ}_{Mg…Free
  3. Q3Which of the following statement is correct? (i) $E_{Cell}$ and $\Delta_r G$ of cell reaction both are extensive properties. (ii) $E_{Cell}$…Free
  4. Q4The difference between the electrode potentials of two electrodes when no current is drawn through the cell is called ___________. (i) Cell…Preview
  5. Q5Which of the following statement is not correct about an inert electrode in a cell? (i) It does not participate in the cell reaction. (ii) I…Preview
  6. Q6An electrochemical cell can behave like an electrolytic cell when ____________. (i) $E_{cell} = 0$ (ii) $E_{cell} > E_{ext}$ (iii) $E_{ext}…Preview
  7. Q7Which of the statements about solutions of electrolytes is not correct? (i) Conductivity of solution depends upon size of ions. (ii) Conduct…Preview
  8. Q8Using the data given below find out the strongest reducing agent. $E^\circ_{Cr_2O_7^{2-}/Cr^{3+}} = 1.33\ V$; $E^\circ_{Cl_2/Cl^-} = 1.36\ V…Preview
  9. Q9Use the data given in Q.8 ($E^\circ_{Cr_2O_7^{2-}/Cr^{3+}} = 1.33\ V$; $E^\circ_{Cl_2/Cl^-} = 1.36\ V$; $E^\circ_{MnO_4^-/Mn^{2+}} = 1.51\ V…Preview
  10. Q10Using the data given in Q.8 ($E^\circ_{Cr_2O_7^{2-}/Cr^{3+}} = 1.33\ V$; $E^\circ_{Cl_2/Cl^-} = 1.36\ V$; $E^\circ_{MnO_4^-/Mn^{2+}} = 1.51\…Preview
  11. Q11Use the data given in Q.8 ($E^\circ_{Cr_2O_7^{2-}/Cr^{3+}} = 1.33\ V$; $E^\circ_{Cl_2/Cl^-} = 1.36\ V$; $E^\circ_{MnO_4^-/Mn^{2+}} = 1.51\ V…Preview
  12. Q12Use the data of Q.8 ($E^\circ_{Cr_2O_7^{2-}/Cr^{3+}} = 1.33\ V$; $E^\circ_{Cl_2/Cl^-} = 1.36\ V$; $E^\circ_{MnO_4^-/Mn^{2+}} = 1.51\ V$; $E^…Preview
  13. Q13The quantity of charge required to obtain one mole of aluminium from $Al_2O_3$ is ___________. (i) $1F$ (ii) $6F$ (iii) $3F$ (iv) $2F$Preview
  14. Q14The cell constant of a conductivity cell _____________. (i) changes with change of electrolyte. (ii) changes with change of concentration of…Preview
  15. Q15While charging the lead storage battery ______________. (i) $PbSO_4$ anode is reduced to $Pb$. (ii) $PbSO_4$ cathode is reduced to $Pb$. (ii…Preview
  16. Q16$\Lambda^0_{m(NH_4OH)}$ is equal to ______________. (i) $\Lambda^0_{m(NH_4OH)} + \Lambda^0_{m(NH_4Cl)} - \Lambda^0_{m(HCl)}$ (ii) $\Lambda^0…Preview
  17. Q17In the electrolysis of aqueous sodium chloride solution which of the half cell reaction will occur at anode? (i) $Na^+(aq) + e^- \rightarrow…Preview
  18. Q18Can absolute electrode potential of an electrode be measured?Preview
  19. Q19Can $E^\circ_{Cell}$ or $\Delta_r G^\circ$ for cell reaction ever be equal to zero?Preview
  20. Q20Under what condition is $E_{Cell} = 0$ or $\Delta_r G = 0$?Preview
  21. Q21What does the negative sign in the expression $E^\circ_{Zn^{2+}/Zn} = -0.76\ V$ mean?Preview
  22. Q22Aqueous copper sulphate solution and aqueous silver nitrate solution are electrolysed by 1 ampere current for 10 minutes in separate electro…Preview
  23. Q23Depict the galvanic cell in which the cell reaction is $Cu + 2Ag^+ \rightarrow 2Ag + Cu^{2+}$Preview
  24. Q24Value of standard electrode potential for the oxidation of $Cl^-$ ions is more positive than that of water, even then in the electrolysis of…Preview
  25. Q25What is electrode potential?Preview
  26. Q26A Daniell (galvanic) cell is used as a power source to run a separate electrolytic cell. In the galvanic cell, a zinc plate dips in ZnSO4 so…Preview
  27. Q27Why is alternating current used for measuring resistance of an electrolytic solution?Preview
  28. Q28A galvanic cell has electrical potential of $1.1\ V$. If an opposing potential of $1.1\ V$ is applied to this cell, what will happen to the…Preview
  29. Q29How will the pH of brine (aq. $NaCl$ solution) be affected when it is electrolysed?Preview
  30. Q30Unlike dry cell, the mercury cell has a constant cell potential throughout its useful life. Why?Preview
  31. Q31Solutions of two electrolytes 'A' and 'B' are diluted. The $\Lambda_m$ of 'B' increases 1.5 times while that of 'A' increases 25 times. Whic…Preview
  32. Q32When acidulated water (dil. $H_2SO_4$ solution) is electrolysed, will the pH of the solution be affected? Justify your answer.Preview
  33. Q33In an aqueous solution how does specific conductivity of electrolytes change with addition of water?Preview
  34. Q34Which reference electrode is used to measure the electrode potential of other electrodes?Preview
  35. Q35Consider a cell given below: $Cu \mid Cu^{2+} \parallel Cl^- \mid Cl_2, Pt$ Write the reactions that occur at anode and cathode.Preview
  36. Q36Write the Nernst equation for the cell reaction in the Daniel cell. How will the $E_{Cell}$ be affected when concentration of $Zn^{2+}$ ions…Preview
  37. Q37What advantage do the fuel cells have over primary and secondary batteries?Preview
  38. Q38Write the cell reaction of a lead storage battery when it is discharged. How does the density of the electrolyte change when the battery is…Preview
  39. Q39Why on dilution the $\Lambda_m$ of $CH_3COOH$ increases drastically, while that of $CH_3COONa$ increases gradually?Preview
  40. Q40Two Daniell-type cells, Cell 'A' and Cell 'B', are connected to each other in opposition (their EMFs oppose). In each cell a zinc electrode…Preview
  41. Q41A galvanic cell is set up as follows: a zinc plate dips in a Zn2+(aq) solution in beaker I, and a silver plate dips in an Ag+(aq) solution i…Preview
  42. Q42What is the relationship between Gibbs free energy of the cell reaction in a galvanic cell and the emf of the cell? When will the maximum wo…Preview
  43. Q43The positive value of the standard electrode potential of $Cu^{2+}/Cu$ indicates that ____________. (Two or more than two options may be cor…Preview
  44. Q44$E^\circ_{cell}$ for some half cell reactions are given below. On the basis of these mark the correct answer. (Two or more than two options…Preview
  45. Q45$E^\circ_{Cell} = 1.1\ V$ for Daniel cell. Which of the following expressions are correct description of state of equilibrium in this cell?…Preview
  46. Q46Conductivity of an electrolytic solution depends on ____________. (Two or more than two options may be correct.) (i) nature of electrolyte.…Preview
  47. Q47$\Lambda^0_{m(H_2O)}$ is equal to _______________. (Two or more than two options may be correct.) (i) $\Lambda^0_{m(HCl)} + \Lambda^0_{m(NaO…Preview
  48. Q48What will happen during the electrolysis of aqueous solution of $CuSO_4$ by using platinum electrodes? (Two or more than two options may be…Preview
  49. Q49What will happen during the electrolysis of aqueous solution of $CuSO_4$ in the presence of $Cu$ electrodes? (Two or more than two options m…Preview
  50. Q50Conductivity $\kappa$, is equal to ____________. (Two or more than two options may be correct.) (i) $\frac{1}{R}\frac{l}{A}$ (ii) $\frac{G^*…Preview
  51. Q51Molar conductivity of ionic solution depends on ___________. (Two or more than two options may be correct.) (i) temperature. (ii) distance b…Preview
  52. Q52For the given cell, $Mg \mid Mg^{2+} \parallel Cu^{2+} \mid Cu$ (Two or more than two options may be correct.) (i) $Mg$ is cathode (ii) $Cu$…Preview
  53. Q53Match the terms given in Column I with the units given in Column II. Column I: (i) $\Lambda_m$ (ii) $E_{Cell}$ (iii) $\kappa$ (iv) $G^*$ Col…Preview
  54. Q54Match the terms given in Column I with the items given in Column II. Column I: (i) $\Lambda_m$ (ii) $E^\circ_{Cell}$ (iii) $\kappa$ (iv) $\D…Preview
  55. Q55Match the items of Column I and Column II. Column I: (i) Lead storage battery (ii) Mercury cell (iii) Fuel cell (iv) Rusting Column II: (a)…Preview
  56. Q56Match the items of Column I and Column II. Column I: (i) $\kappa$ (ii) $\Lambda_m$ (iii) $\alpha$ (iv) $Q$ Column II: (a) $I \times t$ (b) $…Preview
  57. Q57Match the items of Column I and Column II. Column I: (i) Lechlanche cell (ii) Ni–Cd cell (iii) Fuel cell (iv) Mercury cell Column II: (a) ce…Preview
  58. Q58Match the items of Column I and Column II on the basis of data given below: $E^\circ_{F_2/F^-} = 2.87\ V$, $E^\circ_{Li^+/Li} = -3.5\ V$, $E…Preview
  59. Q59Assertion: $Cu$ is less reactive than hydrogen. Reason: $E^\circ_{Cu^{2+}/Cu}$ is negative. (i) Both assertion and reason are true and the r…Preview
  60. Q60Assertion: $E_{Cell}$ should have a positive value for the cell to function. Reason: $E_{cathode} < E_{anode}$ (i) Both assertion and reason…Preview
  61. Q61Assertion: Conductivity of all electrolytes decreases on dilution. Reason: On dilution number of ions per unit volume decreases. (i) Both as…Preview
  62. Q62Assertion: $\Lambda_m$ for weak electrolytes shows a sharp increase when the electrolytic solution is diluted. Reason: For weak electrolytes…Preview
  63. Q63Assertion: Mercury cell does not give steady potential. Reason: In the cell reaction, ions are not involved in solution. (i) Both assertion…Preview
  64. Q64Assertion: Electrolysis of $NaCl$ solution gives chlorine at anode instead of $O_2$. Reason: Formation of oxygen at anode requires overvolta…Preview
  65. Q65Assertion: For measuring resistance of an ionic solution an AC source is used. Reason: Concentration of ionic solution will change if DC sou…Preview
  66. Q66Assertion: Current stops flowing when $E_{Cell} = 0$. Reason: Equilibrium of the cell reaction is attained. (i) Both assertion and reason ar…Preview
  67. Q67Assertion: $E_{Ag^+/Ag}$ increases with increase in concentration of $Ag^+$ ions. Reason: $E_{Ag^+/Ag}$ has a positive value. (i) Both asser…Preview
  68. Q68Assertion: Copper sulphate can be stored in zinc vessel. Reason: Zinc is less reactive than copper. (i) Both assertion and reason are true a…Preview

Sample & Board Papers

Sample papers and previous-year board questions for this subject.