NCERT Solutions for Class 12 Chemistry Chapter 2 Electrochemistry
NCERT Solutions for Class 12 Chemistry Chapter 2 Electrochemistry provides complete coverage of galvanic cells, Nernst equation, conductance in electrolytic solutions, Kohlrausch's law, Faraday's laws of electrolysis, batteries, fuel cells, and corrosion.
Overview of Topics & Subtopics (Click to Jump)
1. Electrochemical Cells, EMF & Nernst Equation
Short Note:
• Galvanic Cell (Voltaic Cell): Device converting chemical energy stored in a spontaneous redox reaction into electrical energy (e.g., Daniell Cell: $\text{Zn(s)} + \text{Cu}^{2+}\text{(aq)} \rightarrow \text{Zn}^{2+}\text{(aq)} + \text{Cu(s)}$).
• Standard Cell Potential ($E^\circ_{\text{cell}}$): $E^\circ_{\text{cell}} = E^\circ_{\text{cathode}} - E^\circ_{\text{anode}}$ (measured against Standard Hydrogen Electrode, $E^\circ = 0\text{ V}$).
• Nernst Equation (at 298 K): Relates cell potential to ion concentration:
$E_{\text{cell}} = E^\circ_{\text{cell}} - \frac{0.0591}{n} \log \frac{[\text{Products}]}{[\text{Reactants}]}$
• Equilibrium Constant ($K_c$) & Gibbs Free Energy ($\Delta G^\circ$):
- $\log K_c = \frac{n \cdot E^\circ_{\text{cell}}}{0.0591}$
- $\Delta G^\circ = -n F E^\circ_{\text{cell}}$ (where $F = 96487\text{ C mol}^{-1} \approx 96500\text{ C mol}^{-1}$)
2. Conductance of Electrolytic Solutions & Kohlrausch's Law
Short Note:
• Conductivity ($\kappa$): Inverse of resistivity ($\kappa = 1/\rho = \frac{1}{R} \cdot \frac{l}{A}$). Unit: $\text{S m}^{-1}$ or $\text{S cm}^{-1}$.
• Molar Conductivity ($\Lambda_m$): Conductance of a solution containing $1\text{ mole}$ of electrolyte:
$\Lambda_m = \frac{\kappa \times 1000}{M}$ (where $M$ is molarity in $\text{mol L}^{-1}$). Unit: $\text{S cm}^2 \text{mol}^{-1}$.
• Variation with Dilution:
- $\kappa$ decreases with dilution because number of ions per unit volume decreases.
- $\Lambda_m$ increases with dilution for both strong and weak electrolytes.
• Kohlrausch's Law of Independent Migration of Ions: At infinite dilution, molar conductivity of an electrolyte is equal to the sum of ionic conductivities of its constituent cations and anions:
$\Lambda_m^\circ = \nu_+ \lambda_+^\circ + \nu_- \lambda_-^\circ$
• Degree of Dissociation ($\alpha$) for Weak Electrolyte: $\alpha = \frac{\Lambda_m}{\Lambda_m^\circ}$
3. Electrolysis, Batteries, Fuel Cells & Corrosion
Short Note:
• Faraday's Laws of Electrolysis:
- 1st Law: Mass deposited $m = Z \cdot Q = Z \cdot I \cdot t$ (where $Z$ is electrochemical equivalent).
- 2nd Law: For same quantity of electricity, masses deposited are proportional to equivalent weights ($m_1 / m_2 = E_1 / E_2$).
• Commercial Batteries:
- Primary Batteries: Cannot be recharged (e.g., Dry Cell, Mercury Cell).
- Secondary Batteries: Rechargeable (e.g., Lead storage battery, Ni-Cd cell).
• Fuel Cells: Devices converting energy from combustion of fuels (like $\text{H}_2, \text{CH}_4$) directly into electrical energy (e.g., $\text{H}_2-\text{O}_2$ fuel cell with ~70% efficiency).
• Corrosion: Electrochemical phenomenon where metal gets oxidized. Anodic region: $\text{Fe(s)} \rightarrow \text{Fe}^{2+} + 2e^-$; Cathodic region: $\text{O}_2 + 4\text{H}^+ + 4e^- \rightarrow 2\text{H}_2\text{O}$. Prevents by sacrificial coating (Galvanization using Zinc).
Intext & Conceptual Questions
• For Strong Electrolytes: Strong electrolytes are completely ionized even at high concentrations. On dilution, interionic interactions decrease, allowing ions to move faster. Thus, $\Lambda_m$ increases slightly with dilution following the Debye-Hückel-Onsager equation: $\Lambda_m = \Lambda_m^\circ - A \sqrt{C}$. A plot of $\Lambda_m$ vs $\sqrt{C}$ gives a straight line with $y$-intercept $\Lambda_m^\circ$.
• For Weak Electrolytes: Weak electrolytes dissociate partially at higher concentrations. Dilution significantly increases the degree of dissociation ($\alpha$). Near infinite dilution, $\alpha \rightarrow 1$, causing a steep, exponential rise in $\Lambda_m$. Hence, $\Lambda_m^\circ$ cannot be obtained by direct extrapolation and must be determined using Kohlrausch's Law.
| Feature | Primary Battery | Secondary Battery |
|---|---|---|
| Rechargeability | Non-rechargeable. Reaction occurs only once. | Rechargeable by passing current in opposite direction. |
| Lifespan | Becomes dead over time after reactants are consumed. | Can undergo several charge-discharge cycles. |
| Examples | Leclanché Dry Cell, Mercury Cell (used in hearing aids). | Lead Storage Battery (automobiles), Nickel-Cadmium Cell. |
Textbook Chapter End Exercise Questions
Given:
• $E^\circ_{\text{cell}} = 0.236\text{ V}$
• Reaction transfers $n = 2$ moles of electrons ($2\text{Fe}^{3+} + 2e^- \rightarrow 2\text{Fe}^{2+}$)
• Faraday constant $F = 96487\text{ C mol}^{-1}$
Step 1: Calculate Standard Gibbs Free Energy ($\Delta G^\circ$)
$\Delta G^\circ = -n F E^\circ_{\text{cell}}$
$\Delta G^\circ = -2 \times 96487 \times 0.236\text{ J mol}^{-1}$
$\Delta G^\circ = -45541.86\text{ J mol}^{-1} \approx -45.54\text{ kJ mol}^{-1}$
Step 2: Calculate Equilibrium Constant ($K_c$)
$\log K_c = \frac{n \cdot E^\circ_{\text{cell}}}{0.0591} = \frac{2 \times 0.236}{0.0591} = 7.986$
$K_c = 10^{7.986} \approx 9.68 \times 10^7$
• $\Delta G^\circ = \mathbf{-45.54\text{ kJ mol}^{-1}}$
• $K_c = \mathbf{9.68 \times 10^7}$
Given:
• Concentration $C = 0.025\text{ mol L}^{-1}$
• Molar conductivity $\Lambda_m = 46.1\text{ S cm}^2 \text{mol}^{-1}$
• $\lambda^\circ(\text{H}^+) = 349.6\text{ S cm}^2 \text{mol}^{-1}$
• $\lambda^\circ(\text{HCOO}^-) = 54.6\text{ S cm}^2 \text{mol}^{-1}$
Step 1: Calculate $\Lambda_m^\circ$ using Kohlrausch's Law
$\Lambda_m^\circ = \lambda^\circ(\text{H}^+) + \lambda^\circ(\text{HCOO}^-)$
$\Lambda_m^\circ = 349.6 + 54.6 = 404.2\text{ S cm}^2 \text{mol}^{-1}$
Step 2: Calculate Degree of Dissociation ($\alpha$)
$\alpha = \frac{\Lambda_m}{\Lambda_m^\circ} = \frac{46.1}{404.2} \approx 0.114$ (or 11.4%)
Step 3: Calculate Dissociation Constant ($K_a$)
$K_a = \frac{C \alpha^2}{1 - \alpha} = \frac{0.025 \times (0.114)^2}{1 - 0.114}$
$K_a = \frac{0.025 \times 0.0130}{0.886} \approx 3.67 \times 10^{-4}\text{ mol L}^{-1}$
• Degree of dissociation ($\alpha$) = 0.114
• Dissociation constant ($K_a$) = 3.67 × 10⁻⁴ mol L⁻¹
Read More & Chapter Resources
These short notes are designed for quick revision. Read the main points once, then use the related material below to practise the same chapter. Revising a concept and checking it with questions can make your preparation more focused.
