આ MCQ મોડ્યુલ આના પર આધારિત છે: Conductance Electrolysis
Conductance Electrolysis
આ મૂલ્યાંકન આના પર આધારિત હશે: Conductance Electrolysis
મૂલ્યાંકન બનાવવામાં તેમની સામગ્રી સામેલ કરવા ચિત્રો, PDF અથવા Word દસ્તાવેજ અપલોડ કરો.
Conductance Electrolysis
2.4 Conductance of Electrolytic Solutions
Metals conduct electricity through mobile electrons. Electrolytes, by contrast, conduct through mobile ions moving in opposite directions when a potential is applied. Measuring how well an ionic solution carries current tells us a great deal about the ions present, their concentration, and the extent to which a weak electrolyte has dissociated.
2.4.1 Resistance, Conductance, Conductivity
For a conductor of length ℓ and cross-sectional area A, the resistance obeys the familiar relation
where ρ (rho) is the resistivity. Unit of R: ohm (Ω). Conductance G is simply the reciprocal: \(G = 1/R\), measured in siemens (S) where 1 S = 1 Ω⁻¹.
The reciprocal of resistivity is the conductivity κ (kappa):
The quantity ℓ/A is called the cell constant (G*) of the conductivity cell and is determined once using a standard KCl solution of known κ.
2.4.2 Molar Conductivity Λm
Conductivity depends on the number of ions per unit volume. To compare electrolytes fairly, we normalise it by concentration:
with c in mol m⁻³, giving Λm in S m² mol⁻¹. A convenient lab form is
2.4.3 How Λm Changes with Dilution
Upon dilution, the number of ions per mole of electrolyte either stays roughly the same (strong electrolyte) or grows (weak electrolyte, because more of it ionises). Either way, Λm rises as c decreases, but the detailed shape of the curve is diagnostic.
Strong electrolytes — Debye–Hückel–Onsager equation
For NaCl, KCl, HCl etc., Λm falls only slightly from its infinite-dilution value Λ°m as concentration increases. The relationship is almost linear in √c:
where A is a constant for a given solvent and temperature. Extrapolating a plot of Λm vs √c to c = 0 gives Λ°m, the limiting molar conductivity.
Weak electrolytes — dramatic rise on dilution
For CH₃COOH, NH₄OH and other weak electrolytes, the low-concentration solution has many more ions (because dilution pushes the dissociation equilibrium forward by Le Chatelier). Λm therefore rises sharply as c → 0 and the √c plot curves upward — the limiting value cannot be reached by simple extrapolation.
2.4.4 Kohlrausch's Law of Independent Migration of Ions
This lets us calculate Λ°m of a weak electrolyte (whose curve cannot be extrapolated) from strong-electrolyte data. For example:
Degree of dissociation & dissociation constant
For a weak electrolyte at concentration c with degree of dissociation α:
Worked Examples — Conductance
A conductivity cell with cell constant 0.367 cm⁻¹ filled with 0.001 M KCl solution shows a resistance of 1500 Ω at 298 K. Find κ and Λm.
Answer: κ = 2.45 × 10⁻⁴ S cm⁻¹; Λm ≈ 245 S cm² mol⁻¹.
Given Λ°m(HCl) = 426, Λ°m(CH₃COONa) = 91, Λ°m(NaCl) = 126 S cm² mol⁻¹, compute Λ°m(CH₃COOH).
Answer: 391 S cm² mol⁻¹ — close to the experimentally accepted value.
The molar conductivity of 0.10 M acetic acid is 5.2 S cm² mol⁻¹. Using Λ°m = 390.5 S cm² mol⁻¹, find α and Ka.
Answer: α ≈ 1.33 %, Ka ≈ 1.8 × 10⁻⁵ — the standard textbook value for CH₃COOH.
2.5 Electrolytic Cells & Electrolysis
Electrolysis is the chemical change driven by passing an electric current through a molten or dissolved electrolyte. An external battery pushes electrons into the cathode (reduction site) and pulls them out of the anode (oxidation site). This is the reverse of what a galvanic cell does.
For instance, passing current through molten NaCl:
produces metallic sodium and chlorine gas — the industrial Downs process.
What actually gets deposited?
In an aqueous solution, several species can be reduced at the cathode or oxidised at the anode. The one that wins depends on:
- Nature of the electrolyte — molten NaCl gives Na at the cathode; aqueous NaCl gives H₂ at the cathode (water is easier to reduce than Na⁺) and Cl₂ at the anode (overvoltage effect).
- Concentration — dilute aqueous NaCl gives O₂ at the anode; concentrated brine gives Cl₂ (this is the chlor-alkali process).
- Nature of the electrode — an inert electrode (Pt, graphite) just transfers electrons; a reactive copper anode in CuSO₄ dissolves preferentially, allowing Cu to be electrorefined.
- Overvoltage — the extra voltage needed to sustain gas evolution. It is why Cl₂ (not O₂) is liberated from concentrated brine despite thermodynamic preference for O₂.
2.5.1 Faraday's Laws of Electrolysis (1833)
The Faraday constant F is the charge on one mole of electrons:
So to deposit one mole of a substance carrying charge n, we must pass n × 96,500 C. For example, reducing 1 mol Cu²⁺ to Cu needs 2F = 193,000 C; depositing 1 mol Al³⁺ needs 3F = 289,500 C.
Applications
- Electroplating: a thin coating of Ag, Au, Ni, Cr on jewellery, car parts — the article is the cathode in a solution of the plating metal's salt.
- Electrometallurgy: extraction of Na, K, Ca, Mg by electrolysing their molten chlorides; Al from molten Al₂O₃ dissolved in cryolite (Hall–Héroult process).
- Electrorefining: impure Cu anode dissolves in CuSO₄ and pure Cu deposits on the cathode; noble impurities (Ag, Au) settle as "anode mud" — often the revenue offset that pays for the process.
- Chlor-alkali industry: concentrated brine → Cl₂(g) + NaOH(aq) + H₂(g).
Worked Examples — Electrolysis
Calculate the mass of Cu deposited when 0.5 A flows through CuSO₄ solution for 30 minutes. (MCu = 63.5 g mol⁻¹)
Charge Q = I × t = 0.5 × 30 × 60 = 900 C. For Cu²⁺ + 2e⁻ → Cu, n = 2 so 2 × 96500 = 193,000 C deposits 63.5 g.
Answer: m ≈ 0.296 g.
How long must a current of 2 A pass through a AgNO₃ solution to deposit 1 g of silver? (MAg = 108, n = 1)
Charge for 1 g Ag = (1/108) × 96500 = 893.5 C. Then t = Q/I = 893.5/2 = 446.8 s ≈ 7.45 min.
Answer: about 7 min 27 s.
How much electric charge is needed to produce 5.4 kg of Al from molten Al₂O₃?
n(Al) = 5400/27 = 200 mol. Each Al³⁺ needs 3 electrons, so mol e⁻ = 600.
Answer: Q ≈ 5.8 × 10⁷ C. This enormous charge demand explains why aluminium smelters are always built beside cheap hydroelectric power.
The same current passes through AgNO₃ and CuSO₄ solutions in series and deposits 1.08 g of Ag. How much Cu is simultaneously deposited?
Equivalent weights: E(Ag) = 108/1 = 108; E(Cu) = 63.5/2 = 31.75.
Answer: 0.32 g Cu.
A current passed through a CuSO₄ cell for 1 hour deposits 1.5 g of Cu. Find the current.
Q = (1.5/63.5) × 2 × 96500 = 4559 C. I = Q/t = 4559/3600 = 1.27 A.
Answer: I ≈ 1.27 A.
- Fill a beaker with 100 mL of 0.5 M CuSO₄ solution.
- Clean an iron key with steel-wool and connect it to the negative terminal of a 4.5 V dry cell.
- Connect a clean copper strip to the positive terminal and dip both into the solution.
- Leave the cell running for 5 min; remove, rinse and dry. Weigh before and after.
Interactive: Electrolysis Calculator L3 Apply
Enter the current, time and metal details. The tool computes the charge and mass deposited using m = (M·I·t)/(n·F), with F = 96,500 C mol⁻¹.
Competency-Based Questions
Q1. L1 Remember The SI unit of specific conductance (κ) is:
Q2. L3 Apply Use Kohlrausch's law to compute Λ°m(CH₃COOH). (2 marks)
Q3. L3 Apply State Faraday's first law and find the mass of silver deposited by 0.965 A current in 1 hour through AgNO₃. (3 marks)
Q4. L3 Apply Why does Λm of a weak electrolyte rise sharply on dilution whereas for a strong electrolyte it changes only slightly? (3 marks)
Q5. L4 Analyse In aqueous NaCl electrolysis with inert electrodes, why is Cl₂ evolved at the anode instead of O₂, even though E°(O₂/H₂O) is lower than E°(Cl₂/Cl⁻)? (3 marks)
Assertion-Reason Questions
Assertion (A): The molar conductivity of a weak electrolyte cannot be obtained by graphical extrapolation of its Λm vs √c plot to c = 0.
Reason (R): At very low concentrations, Λm of a weak electrolyte rises sharply due to increasing dissociation, so the curve does not become linear.
Assertion (A): In an electrolytic cell, the cathode is the negative terminal.
Reason (R): The external source pushes electrons into the cathode to reduce cations.
Assertion (A): Depositing 1 mol of Al needs 3 times as much charge as depositing 1 mol of Ag.
Reason (R): Al³⁺ requires three electrons to become Al, while Ag⁺ needs only one to become Ag.
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