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Chemistry · Class 12 Science

Ch 9Electrochemistry — Class 12 Chemistry, concept-first.

Every material you've ever handled falls into one of three electrical categories: conductor, semiconductor or insulator. Copper and aluminium carry electricity across the country's power grid; the plastic sheathing around the wire keeps that same electricity from going anywhere it shouldn't.

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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

Every material you've ever handled falls into one of three electrical categories: conductor, semiconductor or insulator.

9.1

Conductivity of Electrolytic Solution

An electrolyte such as sodium chloride or potassium chloride, once dissolved in a solvent like water, dissociates almost completely into its constituent cations and anions.

9.1.1

Molar Conductivity

Two solutions at different concentrations contain different numbers of ions per unit volume, and so naturally show different specific conductance — this makes κ a poor basis for comparing how well dif…

9.1.2

Equivalent Conductance

Equivalent conductance, symbol (without the m subscript), is the older, gram-equivalent-based counterpart of molar conductivity, and it remains the natural unit to use whenever a solution's concentrat…

9.1.3

Factors Affecting Electrolytic Conductance

The conductance of an electrolytic solution is not a fixed number for a given electrolyte — it depends on several physical factors that either help or hinder how freely the dissociated ions can move t…

9.1.4

Measurement of Conductivity of Ionic Solutions

Measuring the resistance of a metallic wire with a metre bridge, built on the Wheatstone bridge principle, is a familiar technique from physics practicals; the very same principle, with one crucial mo…

9.2

Variation of Molar Conductivity with Concentration

Friedrich Kohlrausch measured the molar conductance of a range of electrolytes across several concentrations and found a clear, repeatable trend: molar conductance rises as a solution is progressively…

9.2.1

Debye – Hückel and Onsager Equation

At infinite dilution, ions in an electrolytic solution are so far apart that the electrostatic interaction between them becomes negligible.

9.2.2

Kohlrausch's Law

The limiting molar conductance — the value molar conductance approaches at infinite dilution — is the foundation of Kohlrausch's law of independent migration of ions.

9.3

Electrochemical Cell

An electrochemical cell is a device that interconverts chemical energy and electrical energy, built from two separate electrodes each in contact with an electrolyte solution.

9.3.1

Galvanic Cell

Dipping a strip of zinc metal directly into copper sulphate solution causes the blue colour of the solution to fade as red-brown copper metal deposits on the zinc strip — a spontaneous redox reaction,…

9.3.2

Galvanic Cell Notation

Rather than sketch the full apparatus every time a galvanic cell needs to be described, chemists use a compact, standardised line notation — the cell diagram — governed by a small set of IUPAC convent…

9.3.3

EMF of a Cell

When the two half-cells of a Daniel cell are connected, a spontaneous redox reaction drives electrons to flow from the anode to the cathode through the external wire.

9.3.4

Measurement of Electrode Potential

The overall redox reaction inside any electrochemical cell can always be split into two separate half-reactions — an oxidation and a reduction — and correspondingly, the overall cell emf can always be…

9.4

Thermodynamics of Cell Reactions

A galvanic cell converts chemical energy into electrical energy, and the amount of electrical energy it produces can be calculated exactly, once two things are known: the total quantity of electric ch…

9.4.1

Nernst Equation

The Nernst equation relates a cell's potential to the actual concentrations of the species taking part in its electrochemical reaction, rather than assuming they sit fixed at their standard 1 M states…

9.5

Electrolytic Cell and Electrolysis

Electrolysis is the use of electrical energy from an external source to drive a non-spontaneous chemical reaction, most often to decompose a stable compound into its constituent elements.

9.6

Faraday's Laws of Electrolysis

Michael Faraday's two laws of electrolysis put exact numbers on what electrolysis produces, turning it from a qualitative observation into a precise quantitative tool.

9.6.1

First Law

Faraday's first law of electrolysis states that the mass (m) of a substance liberated or deposited at an electrode during electrolysis is directly proportional to the total quantity of electric charge…

9.6.2

Second Law

Faraday's second law compares different electrolytic cells rather than analysing just one: when the SAME quantity of electric charge is passed through the solutions of several different electrolytes (…

9.7

Batteries

Batteries are, at their core, packaged galvanic cells engineered to deliver direct current at a steady, usable voltage, and they are genuinely indispensable to modern life — lithium-ion batteries powe…

9.7.1

Leclanché Cell

The Leclanché cell, more familiarly known as the ordinary dry cell, is the classic primary battery used in torches, remote controls and countless small devices. Its construction is:

9.7.2

Mercury Button Cell

The mercury button cell is a small, flat, long-lasting primary battery valued for its very stable voltage throughout its working life, which makes it well suited to precision devices such as watches,…

9.7.3

Secondary Batteries

A defining feature of secondary batteries is that the electrochemical reactions occurring inside them during discharge can be driven backward by applying an external potential slightly greater than th…

9.7.3.1

Lead Storage Battery

The lead storage battery — familiar as the standard automobile (car) battery — is a secondary (rechargeable) cell whose construction is:

9.7.3.2

The Lithium-ion Battery

The lithium-ion battery is the dominant rechargeable technology inside cell phones, laptops and digital cameras, valued for packing a large amount of energy into a comparatively light, compact cell.

9.8

Fuel Cells

A fuel cell is a special type of galvanic cell in which the energy released by the combustion of a fuel is converted directly into electrical energy, rather than being released as heat the way ordinar…

9.9

Corrosion

The rusting of iron and the dull green film that sometimes forms on copper and brass vessels are both familiar examples of corrosion — a redox process in which a metal is gradually oxidised by atmosph…

9.9.1

Electrochemical Mechanism of Corrosion

Rust formation requires both oxygen AND water together — neither alone is sufficient — and because it is fundamentally an electrochemical redox process, it requires a spatially separated anode and cat…

9.9.2

Protection of Metals from Corrosion

Because corrosion is fundamentally an electrochemical process requiring oxygen, moisture and a favourable electrochemical driving force, every practical protection method works by removing one of thos…

9.10

Electrochemical Series

Standard single electrode potentials are always measured relative to the Standard Hydrogen Electrode, exactly as demonstrated earlier in the worked zinc example.

EVALUATION

52 Q
+Choose the Best Answer25 questions
  1. Q1The number of electrons that have a total charge of 9650 coulombs is (a) $6.22\times10^{23}$ (b) $6.022\times10^{24}$ (c) $6.022\times10^{22…Free
  2. Q2Consider the following half-cell reactions: $\text{Mn}^{2+} + 2e^{-} \rightarrow \text{Mn}$, $E^{o} = -1.18$ V $\text{Mn}^{2+} \rightarrow \…Free
  3. Q3The button cell used in watches functions as follows: $\text{Zn(s)} + \text{Ag}_2\text{O(s)} + \text{H}_2\text{O(l)} \rightleftharpoons 2\te…Free
  4. Q4The molar conductivity of a 0.5 mol dm⁻³ solution of $\text{AgNO}_3$ with electrolytic conductivity of $5.76\times10^{-3}\ \text{S cm}^{-1}$…Preview
  5. Q5| Electrolyte | KCl | KNO₃ | HCl | NaOAc | NaCl | |---|---|---|---|---|---| | $\Lambda^{o}$ (S cm² mol⁻¹) | 149.9 | 145.0 | 426.2 | 91.0 | 1…Preview
  6. Q6Faraday constant is defined as (a) charge carried by 1 electron (b) charge carried by one mole of electrons (c) charge required to deposit o…Preview
  7. Q7How many faradays of electricity are required for the following reaction to occur: $\text{MnO}_4^{-} \rightarrow \text{Mn}^{2+}$ (a) 5F (b)…Preview
  8. Q8A current strength of 3.86 A was passed through molten calcium oxide for 41 minutes and 40 seconds. The mass of calcium in grams deposited a…Preview
  9. Q9During electrolysis of molten sodium chloride, the time required to produce 0.1 mole of chlorine gas using a current of 3 A is (a) 55 minute…Preview
  10. Q10The number of electrons delivered at the cathode during electrolysis by a current of 1 A in 60 seconds is (charge of electron = $1.6\times10…Preview
  11. Q11Which of the following electrolytic solutions has the least specific conductance? (a) 2N (b) 0.002N (c) 0.02N (d) 0.2NPreview
  12. Q12While charging a lead storage battery, (a) $\text{PbSO}_4$ on cathode is reduced to Pb (b) $\text{PbSO}_4$ on anode is oxidised to $\text{Pb…Preview
  13. Q13Among the following cells: I) Leclanché cell II) Nickel–Cadmium cell III) Lead storage battery IV) Mercury cell Primary cells are (a) I and…Preview
  14. Q14Zinc can be coated on iron to produce galvanized iron, but the reverse is not possible. It is because (a) Zinc is lighter than iron (b) Zinc…Preview
  15. Q15Assertion: Pure iron, when heated in dry air, is converted to a layer of rust. Reason: Rust has the composition $\text{Fe}_3\text{O}_4$. (a)…Preview
  16. Q16In the $\text{H}_2\text{-O}_2$ fuel cell, the reaction that occurs at the cathode is (a) $\text{O}_2\text{(g)} + 2\text{H}_2\text{O(l)} + 4e…Preview
  17. Q17The equivalent conductance of a M/36 solution of a weak monobasic acid is 6 mho cm² equivalent⁻¹, and at infinite dilution is 400 mho cm² eq…Preview
  18. Q18A conductivity cell has been calibrated with a 0.01M, 1:1 electrolytic solution (specific conductance $\kappa = 1.25\times10^{-3}\ \text{S c…Preview
  19. Q19Conductivity of a saturated solution of a sparingly soluble salt AB (1:1 electrolyte) at 298 K is $1.85\times10^{-5}\ \text{S m}^{-1}$. Solu…Preview
  20. Q20In the electrochemical cell $\text{Zn} \mid \text{ZnSO}_4\text{(0.01M)} \ \| \ \text{CuSO}_4\text{(1.0M)} \mid \text{Cu}$, the emf of this D…Preview
  21. Q21Consider the change in oxidation state of bromine corresponding to different emf values as shown in the diagram below: $\text{BrO}_4^{-} \xr…Preview
  22. Q22For the cell reaction $2\text{Fe}^{3+}\text{(aq)} + 2\text{I}^{-}\text{(aq)} \rightarrow 2\text{Fe}^{2+}\text{(aq)} + \text{I}_2\text{(aq)}$…Preview
  23. Q23A certain 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 sa…Preview
  24. Q24A gas X at 1 atm is bubbled through a solution containing a mixture of 1M $Y^{-}$ and 1M $Z^{-}$ at 25°C. If the reduction potential order i…Preview
  25. Q25Cell equation: $A + 2B^{+} \rightarrow A^{2+} + 2B$ $A^{2+} + 2e^{-} \rightarrow A$, $E^{o} = +0.34$ V, and $\log_{10}K = 15.6$ at 300 K for…Preview
+Write Brief Answer27 questions
  1. Q1Define anode and cathode.Free
  2. Q2Why does the conductivity of a solution decrease on dilution of the solution?Free
  3. Q3State Kohlrausch's law. How is it useful to determine the molar conductivity of a weak electrolyte at infinite dilution?Free
  4. Q4Describe the electrolysis of molten NaCl using inert electrodes.Preview
  5. Q5State Faraday's Laws of electrolysis.Preview
  6. Q6Describe the construction of the Daniel cell. Write the cell reaction.Preview
  7. Q7Why is the anode in a galvanic cell considered to be the negative electrode and the cathode the positive electrode?Preview
  8. Q8The conductivity of a 0.01M solution of a 1:1 weak electrolyte at 298 K is $1.5\times10^{-4}\ \text{S cm}^{-1}$. i) molar conductivity of th…Preview
  9. Q9Which of 0.1M HCl and 0.1M KCl do you expect to have greater $\Lambda_m^{o}$, and why?Preview
  10. Q10Arrange the following solutions in decreasing order of specific conductance. i) 0.01M KCl ii) 0.005M KCl iii) 0.1M KCl iv) 0.25M KCl v) 0.5M…Preview
  11. Q11Why is AC current used instead of DC in measuring the electrolytic conductance?Preview
  12. Q120.1M 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 a greate…Preview
  13. Q13A current of 1.608 A is passed through 250 mL of a 0.5M solution of copper sulphate for 50 minutes. Calculate the strength of $\text{Cu}^{2+…Preview
  14. Q14Can $\text{Fe}^{3+}$ oxidise bromide to bromine under standard conditions? Given: $E^{o}_{\text{Fe}^{3+}/\text{Fe}^{2+}} = 0.771$ V, $E^{o}_…Preview
  15. Q15Is it possible to store copper sulphate in an iron vessel for a long time? Given: $E^{o}_{\text{Cu}^{2+}/\text{Cu}} = 0.34$ V and $E^{o}_{\t…Preview
  16. Q16Two metals $M_1$ and $M_2$ have reduction potential values of $-x$ V and $+y$ V respectively. Which will liberate $\text{H}_2$ from $\text{H…Preview
  17. Q17Reduction potentials of two metals $M_1$ and $M_2$ are $E^{o}_{M_1^{2+}/M_1} = -2.3$ V and $E^{o}_{M_2^{2+}/M_2} = 0.2$ V. Predict which one…Preview
  18. Q18Calculate the standard emf of the cell $\text{Cd} \mid \text{Cd}^{2+} \ \| \ \text{Cu}^{2+} \mid \text{Cu}$ and determine the cell reaction.…Preview
  19. Q19In a fuel cell, $\text{H}_2$ and $\text{O}_2$ react to produce electricity. In the process, $\text{H}_2$ gas is oxidised at the anode and $\…Preview
  20. Q20The same amount of electricity was passed through two separate electrolytic cells containing solutions of nickel nitrate and chromium nitrat…Preview
  21. Q21A copper electrode is dipped in 0.1M copper sulphate solution at 25°C. Calculate the electrode potential of copper. Given: $E^{o}_{\text{Cu}…Preview
  22. Q22For the cell $\text{Mg(s)} \mid \text{Mg}^{2+}\text{(aq)} \ \| \ \text{Ag}^{+}\text{(aq)} \mid \text{Ag(s)}$, calculate the equilibrium cons…Preview
  23. Q23$9.2\times10^{12}$ litres of water is available in a lake. A power reactor using the electrolysis of water in the lake produces electricity…Preview
  24. Q24Derive an expression for the Nernst equation.Preview
  25. Q25Write a note on sacrificial protection.Preview
  26. Q26Explain the function of the $\text{H}_2\text{-O}_2$ fuel cell.Preview
  27. Q27Ionic conductance at infinite dilution of $\text{Al}^{3+}$ and $\text{SO}_4^{2-}$ are 189 and 160 mho cm² equiv⁻¹ respectively. Calculate th…Preview

Sample & Board Papers

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

+Show 21 questions21 questions
  1. Q1Write short note on chrome plating.Preview
  2. Q2The e.m.f. of the half cell $Cu^{2+}_{(aq)}/Cu_{(s)}$ containing 0.01 M $Cu^{2+}$ solution is $+0.301$ V. Calculate the standard e.m.f. of t…Preview
  3. Q3Determine the standard emf of the cell and standard free energy change of the cell reaction $Zn\,|\,Zn^{2+}\,\|\,Ni^{2+}\,|\,Ni$. The standa…Preview
  4. Q4(a) Give the evidences in favour of Arrhenius theory of electrolytic dissociation. (b) Derive Nernst equation.Preview
  5. Q5The metals near the bottom of the electrochemical series are : (a) Weak reducing agents (b) Weak oxidising agents (c) Strong oxidising agent…Preview
  6. Q6Unit of specific conductance : (a) $ohm^{-1}$ (b) $ohm^{-1}\,m^2$ (c) $ohm^{-1}\,m^{-1}$ (d) $ohm\,m$Preview
  7. Q7Define standard emf of a cell.Preview
  8. Q8Faraday constant is defined as : (a) Charge required to deposit one mole of substance (b) Charge carried by 1 electron (c) Charge carried by…Preview
  9. Q9What are the factors that affects electrolytic conductance ?Preview
  10. Q10(a) Derive an expression for Nernst equation. **OR** (b) What are the characteristics of catalyst ?Preview
  11. Q11The emf of Standard Hydrogen Electrode (SHE) is ________. (a) $-1.0$ (b) $0$ (c) $1.1$ (d) $+1.0$Preview
  12. Q12State Faraday's Laws of Electrolysis.Preview
  13. Q13Among the following cells primary cells are : (i) Leclanche cell (ii) Nickel-Cadmium cell (iii) Lead Storage Battery (iv) Mercury cell (a) (…Preview
  14. Q14Can $Fe^{3+}$ oxidise bromide to bromine under Standard Conditions ? Given : $E^{\circ}_{Fe^{3+}|Fe^{2+}} = 0.771\ V$ $E^{\circ}_{Br_2|Br^-}…Preview
  15. Q15(a) (i) Explain about Galvanic cell notation. (ii) Define gold number. **OR** (b) Write notes on Lucas Test.Preview
  16. Q16The number of electrons that have a total charge of 9650 coulombs is : (a) $6.022 \times 10^{22}$ (b) $6.22 \times 10^{23}$ (c) $6.022 \time…Preview
  17. Q17Define Equivalent Conductance.Preview
  18. Q18(a) Derive an expression for Nernst equation. **OR** (b) How will you convert (i) Ethyl alcohol $\rightarrow$ Ethene (ii) Ethylene glycol $\…Preview
  19. Q19Which of the following statements is incorrect ? (a) $Co^{3+}$ and $Fe^{2+}$ have same number of unpaired electrons. (b) Of all the known el…Preview
  20. Q20The molar conductivity of a $0.5\ mol\ dm^{-3}$ solution of $AgNO_3$ with specific conductance $5.76 \times 10^{-3}\,S\,cm^{-1}$ at 298 K is…Preview
  21. Q21(a) (i) Explain the thermodynamics of cell reactions. (ii) Why salt bridge is used in Galvanic cells ? **OR** (b) How does diethyl ether rea…Preview