Q.What will happen during the electrolysis of aqueous solution of CuSO4 in the presence of Cu electrodes? (Two or more than two options may be correct.)
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Faraday's Laws of Electrolysis
Imagine you're trying to plate a copper spoon with silver. You drop the spoon into a solution containing silver ions, connect it to a battery, and wait. How much silver actually deposits? Does it depend on how long you wait? On how strong the battery is? On what metal you're using?
Faraday's laws answer exactly these questions. They connect the invisible world of electrons flowing through a wire to the visible world of atoms depositing on a surface.
The Intuition First
Think of electrolysis as a counting problem. Each silver ion (Ag+) needs exactly one electron to become a neutral silver atom (Ag). So if you push a certain number of electrons through the circuit, you should get exactly that many silver atoms deposited.
The first law says: more charge → more mass deposited. Double the charge, double the mass. It's a direct proportionality.
The second law says: different elements need different amounts of charge per atom. A copper ion (Cu2+) needs two electrons to become neutral copper, so for the same amount of charge, you get half as many copper atoms as silver atoms.
The Precise Statements
First Law: The mass of a substance liberated at an electrode is directly proportional to the quantity of electric charge passed through the electrolyte.
m∝Qorm=ZQ
where Z is the electrochemical equivalent of the substance.
Second Law: When the same quantity of charge is passed through different electrolytes, the masses of substances liberated are proportional to their chemical equivalents (equivalent weights).
E1m1=E2m2
Here E is the equivalent weight: atomic mass divided by the number of electrons transferred per ion (n). For silver (Ag+, n=1), E=107.87 g. For copper (Cu2+, n=2), E=63.55/2=31.77 g.
The Combined Law
These two laws merge into one powerful equation:
m=FQ×E
where F is Faraday's constant — the charge carried by one mole of electrons: F=96485 coulombs per mole.
Since Q=I×t (current × time), you can write:
m=FI×t×E
This is the working formula for every electrolysis calculation in your exams.
To avoid confusion: equivalent weight E is always atomic mass divided by n (the number of electrons gained or lost per ion). For Al3+, n=3; for O2 gas (from water), each oxygen atom loses 2 electrons, but the molecule has 2 atoms, so n=4 per O2 molecule.
A Worked Example
Problem: How much copper deposits when a current of 2.0 A flows through a copper sulfate solution for 30 minutes? (Atomic mass of Cu = 63.5 g/mol, n=2)
Step 1: Find the equivalent weight.
E=263.5=31.75 g/mol
Step 2: Find total charge.
Q=I×t=2.0×(30×60)=3600 C
Step 3: Apply the combined law.
m=FQ×E=964853600×31.75=1.185 g
So about 1.2 grams of copper deposits. …
Why this formula?
Faraday's Laws of Electrolysis: Why the Formulas Hold
Faraday's Laws of Electrolysis describe the quantitative relationship between the amount of electricity passed through an electrolyte and the mass of substance liberated at the electrodes. Let's build the reasoning step-by-step.
1. The Core Idea: Charge Carries Matter
Electrolysis works because ions (charged particles) move toward electrodes and undergo redox reactions.
- At the cathode (negative electrode), cations gain electrons (reduction).
- At the anode (positive electrode), anions lose electrons (oxidation).
The key insight: Each ion that reacts carries a fixed amount of charge.
- For a monovalent ion (e.g., Na+), charge = 1.602×10−19C (the elementary charge e).
- For a divalent ion (e.g., Cu2+), charge = 2e.
Thus, the total charge passed (Q) is directly proportional to the number of ions that have reacted (N):
Q=N⋅ze
where:
- z = valency (number of electrons transferred per ion)
- e = elementary charge (1.602×10−19C)
2. From Number of Ions to Mass
The number of ions N is related to the mass (m) of substance liberated via Avogadro's number (NA) and molar mass (M):
N=Mm⋅NA
Substitute into Q=Nze:
Q=(Mm⋅NA)⋅ze
3. Introducing Faraday's Constant
The product NAe appears repeatedly — it's called Faraday's constant (F):
F=NAe≈96485C mol−1
So:
Q=Mm⋅zF
Rearrange for mass:
m=zFQM
This is the unified formula for both of Faraday's laws.
4. Why Two "Laws"? — They Are the Same Idea
Faraday originally stated two laws, but they are logical consequences of the same charge–mass relationship:
First Law (Direct Proportionality)
Mass liberated is directly proportional to the charge passed.
From m=zFQM, if M, z, and F are constant, then:
m∝Q
Why? Because each ion needs a fixed charge to react — more charge means more ions, hence more mass.
Second Law (Electrochemical Equivalent)
For the same charge, masses liberated are proportional to equivalent weights.
Equivalent weight E=zM (mass per mole of electrons transferred).
From m=FQ⋅zM=FQ⋅E, if Q is fixed:
m∝E
Why? For the same charge, the number of electrons transferred is fixed. A substance with a smaller z (fewer electrons per ion) will liberate more moles of substance, hence more mass per mole.
5. Practical Formula for Exams …
The key idea is Faraday's laws of electrolysis applied to an electrolytic cell with active (copper) electrodes. Unlike inert electrodes, the copper anode itself can participate in the reaction.
-
Cathode reaction: Cu2+ ions in solution gain electrons and deposit as copper metal:
Cu2++2e−→Cu(s) — so copper deposits at the cathode.
-
Anode reaction: Since the anode is made of copper, it can oxidise (dissolve) more easily than any anion in solution (like SO42− or OH−). The reaction is: …
In the electrolysis of aqueous CuSO4 with copper electrodes, the anode itself is oxidised (copper dissolves) and Cu2+ ions from the solution are reduced at the cathode (copper deposits). No gas evolution occurs. The correct options are (i) and (ii).
This is a classic case of electrolysis with active electrodes. The key idea is that when the electrodes are made of the same metal as the cation in the electrolyte, the electrode reactions change completely — the anode is no longer inert, so it participates in the reaction.
Let’s break it down.
1. What are the species present in the solution?
Aqueous CuSO4 dissociates into Cu2+ and SO42− ions. Water itself is also present, providing H+ and OH− ions (though in very low concentration).
So at the electrodes, we have competing possibilities:
- At cathode (reduction): Cu2+ ions can be reduced to Cu metal, or H+ from water can be reduced to H2 gas.
- At anode (oxidation): SO42− ions can be oxidised (very difficult), OH− from water can be oxidised to O2 gas, or the copper metal of the anode itself can be oxidised to Cu2+.
The standard reduction potentials tell us which reaction is favoured.
2. Why copper deposits at the cathode — not hydrogen
The reduction potentials (at 298 K, 1 M, vs SHE) are:
Cu2++2e−→Cu(s)E∘=+0.34 V
2H++2e−→H2(g)E∘=0.00 V
A more positive E∘ means a greater tendency to be reduced. Cu2+ reduction is much more favourable than H+ reduction. So at the cathode, copper ions are reduced to copper metal, which deposits on the cathode.
A common mistake is to think that because water is present, hydrogen gas must evolve. But unless the Cu2+ concentration is extremely low, copper deposition is strongly favoured. In standard conditions, copper plates out first.
So option (i) Copper will deposit at cathode is correct.
3. What happens at the anode — the crucial difference
If the anode were inert (like platinum or graphite), the only possible oxidation would be of OH− to O2:
4OH−→O2+2H2O+4e−E∘=+0.40 V
But here the anode is copper metal. Copper can itself be oxidised:
Cu(s)→Cu2++2e−E∘=−0.34 V
The oxidation potential (the reverse of the reduction potential) is +0.34 V for copper dissolution, compared to +0.40 V for oxygen evolution. A lower oxidation potential means the reaction is easier. So copper metal from the anode dissolves into the solution as Cu2+ ions, rather than oxygen being produced. …
Method: Electrode Potential Comparison for Electrolysis (Active Electrodes)
This method uses standard oxidation/reduction potentials, but with an added check: whether the electrode material itself can react (an "active" electrode) instead of only the ions in solution.
Steps:
-
List the species present.
Aqueous CuSO4 with copper electrodes: Cu2+, SO42−, water — and, crucially, the copper metal of the electrodes themselves.
-
At the cathode, compare reduction potentials:
- Cu2++2e−→Cu(s); E∘=+0.34 V
- 2H++2e−→H2(g); E∘=0.00 V
Cu2+ reduction is more favourable, so copper deposits at the cathode.
-
At the anode, first check whether the electrode itself can be oxidised.
Because this anode is copper metal (an "active" electrode, not inert Pt/graphite), compare:
- Cu(s)→Cu2++2e−; Eox∘=+0.34 V
- 4OH−→O2+2H2O+4e−; Eox∘≈+0.40 V …
Here are the most common mistakes students make on this exact type of "active electrode electrolysis" question, along with how to avoid each.
1. Assuming Oxygen Is Released at the Anode, As With Inert Electrodes
The Mistake:
Students remember that with Pt/graphite electrodes, water is oxidised to O2 at the anode, and wrongly apply the same conclusion here.
How to Avoid:
Always check the electrode material first. If the anode is made of the same metal as the cation in solution (copper anode in CuSO4), the metal itself is oxidised in preference to water — no gas is evolved at all.
2. Forgetting to Compare the Electrode's Own Oxidation Potential
The Mistake:
Students only compare SO42− and H2O as candidates for anode oxidation, never considering that the copper electrode itself can be oxidised.
How to Avoid:
Write out Cu(s)→Cu2++2e− (Eox∘=+0.34 V) alongside 4OH−→O2+2H2O+4e− (Eox∘≈+0.40 V). The lower oxidation potential (copper) is favoured, so the anode dissolves instead of evolving oxygen.
3. Thinking Copper Can Deposit at the Anode
The Mistake:
Students pick "copper deposits at anode" because copper is visibly involved at both electrodes.
How to Avoid:
Deposition is always a reduction process, and the anode is always where oxidation occurs. Copper metal is produced by oxidation (dissolves) at the anode, and consumed by reduction (deposits) only at the cathode — never the reverse.
4. Missing the Real-World Link to Electrorefining
The Mistake:
Students don't connect this setup to a named process, so they can't sanity-check their answer.
How to Avoid: …
- COMEDK 2026Set 2026-A1 markMCQQ.The quantity of Ca that can be produced from molten CaCl2, with the same quantity of electricity (in coulombs) required to produce 4.8 g of Mg from molten MgCl2 is: [Atomic mass of Mg=24u; Atomic mass of Ca=40u ] (A) 5.2 g (B) 6.0 g (C) 8.0 g (D) 4.8 g
›Reveal solutionSolution
The key idea is that equal quantities of electricity produce equal moles of electrons, so the mass of metal produced is proportional to its equivalent weight. Since both Mg and Ca are divalent, the mass of Ca produced is (40/24) × 4.8 g = 8.0 g.
Concept and Intuition
This problem is about Faraday’s laws of electrolysis. The same amount of charge (coulombs) will liberate the same number of moles of electrons. For a metal ion Mn+, the number of moles of metal produced is (moles of electrons) / n. So the mass of metal = (charge / (nF)) × atomic mass. Since the charge is the same for both, the mass ratio of two metals is simply (atomic mass₁ / n₁) : (atomic mass₂ / n₂). Here both Mg and Ca form +2 ions, so n is the same (2), and the mass ratio equals the atomic mass ratio.
Step-by-step reasoning
- Identify the relevant half-reactions In molten MgCl2, magnesium ions are reduced:
Mg2++2e−→Mg
In molten CaCl2, calcium ions are reduced:
Ca2++2e−→Ca
Both require 2 moles of electrons per mole of metal.
- Find moles of Mg produced Given mass of Mg = 4.8 g, atomic mass = 24 g/mol.
Moles of Mg=244.8=0.20 mol
- Find moles of electrons used Each mole of Mg requires 2 moles of electrons.
Moles of electrons=0.20×2=0.40 mol
- Same charge means same moles of electrons for Ca The same quantity of electricity provides 0.40 mol of electrons. Each mole of Ca also requires 2 moles of electrons.
- COMEDK 2026Set 2026-M1 markMCQQ.3.482×10−1 g of Fe gets deposited when an aqueous solution of Ferric sulphate is electrolysed for 20 minutes using a current of " x " amperes. Find " x ". (Atomic mass of Fe=56amu ). (A) 2.4 A (B) 2.8 A (C) 0.98 A (D) 1.5 A
›Reveal solutionSolution
This is a Faraday’s law problem where iron is deposited from Fe³⁺ ions. The key is that each Fe³⁺ requires 3 moles of electrons to become Fe(s). Using the mass deposited, time, and atomic mass, we solve for current. The answer is 1.5 A.
Concept & Intuition
Electrolysis is about forcing a non-spontaneous redox reaction with electricity. The amount of substance deposited at an electrode is directly proportional to the charge passed. Faraday’s law says:
m=n⋅FQ⋅M
where m = mass deposited, Q = total charge (current × time), M = molar mass, n = number of electrons per ion, and F = Faraday constant (96485 C/mol).
Here, ferric sulphate gives Fe³⁺ ions. Each Fe³⁺ gains 3 electrons to become Fe metal:
Fe3++3e−→Fe(s)
So n=3. The pitfall? Many students mistakenly use n=2 (thinking of Fe²⁺) or forget to convert time to seconds.
Step-by-step solution
- Identify the half-reaction and n Ferric ion is Fe³⁺. Reduction to metal:
Fe3++3e−→Fe
Hence, n=3 moles of electrons per mole of Fe.
- Write Faraday’s law
m=n⋅FI⋅t⋅M
where I = current (A), t = time (s), M = atomic mass (g/mol), F=96485C/mol.
-
Convert given data to consistent units
- Mass: m=3.482×10−1g=0.3482g
- Time: t=20min=20×60=1200s
- Atomic mass: M=56g/mol
- n=3
- F=96485C/mol
-
Solve for current I
Rearranging:
I=t⋅Mm⋅n⋅F
Substitute values:
- COMEDK 2025Set 2025-A1 markMCQQ.A current of 1.5 A is passed for 2 hours through an aqueous solution of PdXnn where X is a monovalent anion. During the electrolysis process 2.977 g of Palladium metal gets deposited at the cathode. Calculate the charge on Pd ions. (Atomic mass of Pd=106.4 g/mol ). (A) n=4 (B) n=6 (C) n=3 (D) n=2
›Reveal solutionSolution
The charge on the Pd ion is found by equating the total charge passed (from current and time) to the charge required to deposit the given mass of Pd, using Faraday’s laws. The result shows the ion carries a +4 charge, so the correct option is (A).
Concept & Intuition
Electrolysis is governed by Faraday’s laws: the mass of a substance deposited at an electrode is proportional to the total charge passed. For a metal ion Pdn+, the reduction reaction is
Pdn++ne−→Pd
So each mole of Pd deposited consumes n moles of electrons. By calculating the total charge passed and the moles of Pd deposited, we can solve for n, the charge number (oxidation state) of the palladium ion.
-
Calculate total charge passed
Current I=1.5A, time t=2hours=2×3600=7200s.
Charge Q=I×t=1.5×7200=10800C.
-
Calculate moles of Pd deposited
Mass deposited m=2.977g, atomic mass M=106.4g/mol.
Moles of Pd:
moles=106.42.977≈0.02798mol
- Relate charge to moles of electrons Faraday’s constant F=96485C/mol e−. Total moles of electrons used:
-
- COMEDK 2025Set 2025-M1 markMCQQ.A current of 2.5 amperes is passed through 800 ml of 0.48 M solution of CuSO4 for 1.0 hour with a current efficiency of 80%. If the volume of the solution remains unchanged, what is the final molarity of the solution? (A) 0.386 (B) 0.315 (C) 0.433 (D) 0.298
›Reveal solutionSolution
Effective charge =7200 C deposits 0.0373 mol Cu2+; remaining Cu2+ in the unchanged 0.8 L gives molarity ≈0.433 M — option (C).
Effective charge passed (80% current efficiency)
Q=Itη=2.5 A×3600 s×0.80=7200 C.
Moles of Cu2+ deposited — Cu2++2e−→Cu:
ne−=965007200=0.0746 mol,nCu=20.0746=0.0373 mol.
Remaining Cu2+ …
- COMEDK 2024Set 2024-A1 markMCQQ.When 0.1 mole of MnO42− is oxidised, the quantity of electricity required to completely oxidise MnO42− to MnO4− is (A) 96500 C (B) 48250 C (C) 9650 C (D) 2 × 96500 C
›Reveal solutionSolution
MnO42−→MnO4− is a one-electron oxidation (Mn goes +6 → +7), so 0.1 mol requires 0.1×F=0.1×96500=9650 C.
Manganese changes oxidation state from +6 in MnO42− to +7 in MnO4−, i.e. loss of 1 electron per ion: …
- COMEDK 2024Set 2024-E1 markMCQQ.What is the quantity of charge, in Faraday units, required for the reduction of 3.5 moles of Cr2O72− in acid medium? (A) 6.0 (B) 10.5 (C) 21.0 (D) 3.0
›Reveal solutionSolution
The key is to find the total change in oxidation number per mole of dichromate, then multiply by moles and convert to Faradays. For 3.5 moles of Cr2O72− reduced to Cr3+ in acid, the charge required is 21.0 Faradays, so the correct option is (C).
Concept & Intuition
In electrochemistry, one Faraday (F) is the charge carried by one mole of electrons — about 96,485 coulombs. When we talk about "reduction" of an ion, we mean it gains electrons. The number of Faradays needed equals the total moles of electrons transferred. So the problem reduces to: How many electrons does one dichromate ion take up when it is reduced in acid? That number comes from the change in oxidation state of chromium.
Step-by-step solution
-
Determine the oxidation state of Cr in dichromate
In Cr2O72−, oxygen is always -2 (except in peroxides). Let the oxidation state of Cr be x.
For the ion: 2x+7(−2)=−2
⇒2x−14=−2⇒2x=+12⇒x=+6.
So each Cr is in the +6 state.
-
Identify the reduction product in acid medium
In acidic solution, dichromate is reduced to chromium(III) ions, Cr3+.
So each Cr goes from +6 to +3, a gain of 3 electrons per Cr atom.
-
Electrons per dichromate ion
Since one Cr2O72− contains two Cr atoms, the total electrons gained per ion is 2×3=6 electrons.
-
Total electrons for 3.5 moles
For 3.5 moles of dichromate:
moles of electrons=3.5×6=21.0 moles of electrons. …
-
- COMEDK 2024Set 2024-E1 markMCQQ.A current of 3.0A is passed through 750 ml of 0.45 M solution of CuSO4 for 2 hours with a current efficiency of 90%. If the volume of the solution is assumed to remain constant, what would be the final molarity of CuSO4 solution? (A) 0.296 (B) 0.4 (C) 0.237 (D) 0.316
›Reveal solutionSolution
Effective charge 19440 C deposits 0.1007 mol Cu; remaining Cu2+=0.3375−0.1007=0.2368 mol in 0.75 L → 0.316 M.
Effective charge passed (90% efficiency):
Q=Itη=3.0×(2×3600)×0.90=19440 C
Moles of electrons:
ne=9650019440=0.2015 mol
Copper deposited (Cu2++2e−→Cu):
nCu=20.2015=0.1007 mol …
- COMEDK 2024Set 2024-M1 markMCQQ.Propane in presence of O2 gas undergoes complete combustion to produce CO2 and H2O. The required O2 for this combustion reaction was produced by the electrolysis of water. For what duration of time had water been electrolysed by passing 200 A current so that Oxygen gas produced could completely burn 44 g of Propane? (A) 2.68 hours (B) 1.98 hours (C) 3.86 hours (D) 1.34 hours
›Reveal solutionSolution
Burning 44 g (1 mol) of propane needs 5 mol of O2; producing that much O2 by electrolysis takes 20 mol of electrons, i.e. t=20020×96500=9650 s=2.68 hours — option (A).
Step 1 — Combustion stoichiometry
C3H8+5O2→3CO2+4H2O
Moles of propane =4444=1 mol, so O2 required =5 mol.
Step 2 — Electrons needed to make 5 mol O2
At the anode during water electrolysis:
2H2O→O2+4H++4e− …
- COMEDK 2023Set 2023-E1 markMCQQ.If electrolysis of water is carried out for a time duration of 2 hours, how much electric current in amperes would be required to liberate 100 ml of O2 gas measured under standard conditions of temperature and pressure? (A) 0.1723 A (B) 4.178 A (C) 0.8616 A (D) 0.2393 A
›Reveal solutionSolution
Current (t = 2 h = 7200 s): I = Q/t = 1723 / 7200 = 0.2393 A
Concept: Faraday's laws. At the anode in the electrolysis of water:
2 H2O -> O2 + 4 H+ + 4 e-
So 4 mol of electrons (4 F) liberate 1 mol O2.
Moles of O2 at STP:
n(O2) = 0.100 L / 22.4 L/mol = 4.464 x 10^-3 mol
Charge required:
n(e-) = 4 x 4.464 x 10^-3 = 1.786 x 10^-2 mol …
- COMEDK 2023Set 2023-M1 markMCQQ.Assuming no change in volume, the time required to obtain solution of pH=4 by electrolysis of 100 mL of 0.1 M NaOH (using current 0.5 A ) will be (A) 1.93 s (B) 2.63 s (C) 1.80 s (D) 4.26 s
›Reveal solutionSolution
Reaching pH=4 requires generating H+ (10−4M in 0.1L=10−5mol). Since each H+ needs one electron (Q=nF), t=nF/I=(10−5×96500)/0.5≈1.93, matching option (A).
At the anode, electrolysis of the aqueous solution generates H+:
2H2O→O2+4H++4e−,so moles of H+=moles of e−.
Target: pH=4⇒[H+]=10−4M in 100mL=0.1L:
nH+=10−4×0.1=10−5mol.
Charge required (Faraday's law): …
- KCET 2022Set B-31 markMCQQ.In Fuel cells ______ are used as catalysts. (A) Zinc - Mercury (B) Lead - Manganese (C) Platinum - Palladium (D) Nickel - Cadmium
›Reveal solutionSolution
The NCERT hydrogen–oxygen fuel cell uses finely divided platinum or palladium metal, incorporated into the porous carbon electrodes, as the catalyst.
Step 1 — What a fuel cell is.
A fuel cell is a galvanic cell that converts the energy of combustion of a fuel (here H2) directly into electrical energy, instead of burning it to run a turbine. The classic example is the H2–O2 fuel cell used in the Apollo space programme.
Step 2 — The construction.
H2 and O2 are bubbled through porous carbon electrodes into a concentrated aqueous NaOH (or KOH) electrolyte. To make the electrode reactions fast enough at ordinary temperature, catalysts such as finely divided platinum or palladium metal are incorporated into the electrodes.
Step 3 — The electrode reactions being catalysed.
Anode (oxidation of the fuel):
2H2(g)+4OH−(aq)⟶4H2O(l)+4e−
Cathode (reduction of oxygen):
O2(g)+2H2O(l)+4e−⟶4OH−(aq)
Overall:
2H2(g)+O2(g)⟶2H2O(l) …
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