Q.Aqueous copper sulphate solution and aqueous silver nitrate solution are electrolysed by 1 ampere current for 10 minutes in separate electrolytic cells. Will the mass of copper and silver deposited on the cathode be same or different? Explain your answer.
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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: the mass of a substance deposited at an electrode is proportional to its equivalent weight (E=M/n, where M is molar mass and n is the number of electrons transferred per ion).
Reasoning:
- Same current (1 A) and same time (10 min=600 s) means the same quantity of charge passes through both cells: Q=It=1×600=600 C. …
The mass of copper and silver deposited will be different because the same charge liberates different masses depending on the metal’s equivalent weight (molar mass ÷ n-factor). Silver has a higher equivalent weight than copper, so more silver is deposited.
Why Faraday’s laws answer this directly
When you pass the same current for the same time through two different electrolytic cells connected in series (or run separately with identical current and time), the quantity of charge flowing through each is identical:
Q=I×t=1.0 A×(10×60) s=600 C
Faraday’s first law says: the mass of a substance deposited at an electrode is proportional to the charge passed. But the constant of proportionality depends on the substance — specifically on its electrochemical equivalent Z, which is:
Z=nFM
where M is molar mass, n is the number of electrons transferred per ion (the valency factor), and F=96485 C mol−1 is Faraday’s constant.
So the mass deposited is:
m=Z×Q=nFM×Q
Since Q and F are the same for both cells, the ratio of masses depends only on nM — the equivalent weight.
Step-by-step reasoning
-
Identify the cathode reactions
In aqueous solution:
- Copper sulphate: Cu2++2e−→Cu Here n=2, MCu=63.5 g mol−1.
- Silver nitrate: Ag++e−→Ag Here n=1, MAg=108 g mol−1.
-
Compute the equivalent weights
- Equivalent weight of Cu = 263.5=31.75 g eq−1
- Equivalent weight of Ag = 1108=108 g eq−1
Watch outA common mistake is to compare molar masses directly (63.5 vs 108) and conclude copper deposits less. That’s correct here, but only because silver’s n-factor is smaller. If both had the same n-factor, the comparison would be different.
-
Calculate the masses deposited
Using m=nFM×Q:
- For copper:
mCu=2×9648563.5×600≈0.197 g
- For silver: …
Faraday's Laws of Electrolysis — Solution Method
Method: Faraday's Second Law of Electrolysis (Law of Equivalent Masses)
Step 1: State the Law
Faraday's Second Law states:
When the same quantity of electricity is passed through different electrolytes, the masses of substances deposited are directly proportional to their chemical equivalents (equivalent masses).
Mathematically:
m2m1=E2E1
where:
- m = mass deposited
- E = equivalent mass of the substance
Step 2: Identify the Given Data
- Current (I) = 1 A (same for both cells)
- Time (t) = 10 minutes = 10×60=600 seconds (same for both cells)
- Electrolytes: Aqueous CuSO4 and aqueous AgNO3
Since current and time are identical, the quantity of electricity (Q=I×t) passed is the same for both cells.
Step 3: Find Equivalent Masses
For copper in CuSO4:
- Copper ion: Cu2+ (valency = 2)
- Atomic mass of Cu = 63.5 g/mol
- Equivalent mass ECu=ValencyAtomic mass=263.5=31.75 g/eq
For silver in AgNO3:
- Silver ion: Ag+ (valency = 1)
- Atomic mass of Ag = 108 g/mol
- Equivalent mass EAg=1108=108 g/eq
Step 4: Apply the Law …
Here are the most common mistakes students make when solving this exact type of Faraday's Law electrolysis problem, along with how to avoid each.
1. Forgetting to Convert Time to Seconds
The Mistake:
Students plug in time as 10 minutes directly into the formula Q=I×t, forgetting that the standard unit for time in the formula is seconds.
How to Avoid:
Always write the conversion step explicitly:
t=10 min×60 s/min=600 s
Then use Q=I×t=1×600=600 C (the current given in the question is 1 ampere, not 1.5 A — always re-check the given data before plugging in numbers).
2. Using the Wrong Number of Electrons (n)
The Mistake:
Assuming n=1 for both metals, or guessing without checking the half-reaction. For copper, many students forget that Cu2+ requires 2 electrons to become Cu.
How to Avoid:
Write the cathode half-reactions first:
Cu2++2e−→Cu(n=2)
Ag++e−→Ag(n=1)
Never guess — always write the balanced ionic equation for each metal separately.
3. Using the Wrong Molar Mass
The Mistake:
Using the molar mass of the compound (e.g. CuSO4, 159.6 g/mol) instead of just the metal (63.5 g/mol for Cu, 108 g/mol for Ag).
How to Avoid:
The question asks for the mass of metal deposited, not the mass of the compound. Use MCu=63.5 g/mol and MAg=108 g/mol.
4. Mixing Up Faraday's Constant Value
The Mistake:
Using F=96500 or F=96485 inconsistently, or forgetting to include it in the formula.
How to Avoid:
Memorise:
F=96500 C/mol
Always write the full formula:
m=n×FQ×M
5. Arithmetic Errors — Especially Using the Wrong Given Current
The Mistake:
Rushing through the calculation and substituting the wrong current value (e.g. using 1.5 A when the question states 1 A), which throws off the entire final answer.
How to Avoid:
Do the calculation step-by-step, always re-checking the given data first:
- I=1 A (as stated in the question)
- t=600 s
- Q=I×t=600 C
For copper (M=63.5, n=2, F=96500): …
- GUJCET 2025Set 031 markMCQQ.For the given reaction how much quantity of electricity in Coulomb is required? 32Al2O3→34Al+O2 (A) 6×96500 C (B) 2×96500 C (C) 3×96500 C (D) 4×96500 C
›Reveal solutionSolution
[!TLDR]
Depositing 34 mol of Al needs 4 mol of electrons, i.e. 4×96500 C.
Concept
One mole of electrons carries a charge of 1F=96500 C. The moles of electrons equal (moles of metal) × (electrons per ion), from Faraday's laws of electrolysis.
Solution
The reduction half-reaction is:
Al3++3e−→Al
The equation produces 34 mol Al, so moles of electrons: …
- GUJCET 2024Set 131 markMCQQ.During the electrolysis of higher concentration of H2SO4, the product obtained at anode is ________. (A) O2(g) (B) S2O8(aq)2− (C) SO2(g) (D) SO3(aq)2−
›Reveal solutionSolution
At high H2SO4 concentration, HSO4−/SO42− is oxidised at the anode to peroxodisulphate instead of O2.
Concept: During electrolysis, whether O2 or peroxodisulphate forms at the anode depends on concentration and overpotential. In dilute H2SO4, water is oxidised to O2. In concentrated H2SO4, the sulphate ion is ox …
- GUJCET 2023Set 091 markMCQQ.Which of the following chemical reaction occur at anode during electrolysis of higher concentrated H2SO4 solution? (A) 2SO42−(aq)→S2O82−(aq)+2e− (B) 2H2O(l)→O2(g)+4H(aq)++4e− (C) H2O(l)+e−→21H2(g)+2OH(aq)− (D) S2O82−(aq)+2e−→2SO42−(aq)
›Reveal solutionSolution
[!TLDR]
Concentrated H2SO4 electrolysis gives peroxydisulphate at the anode by oxidation of sulphate.
Concept
At the anode, oxidation (loss of electrons) occurs. With highly concentrated sulphate solutions, sulphate ions are preferentially oxidised to peroxydisulphate rather than water being oxidised to O2.
Solution
In concentrated H2SO4 the high concentration of sulphate favours their oxidation:
2SO42−(aq)→S2O82−(aq)+2e− …
- GUJCET 2022Set 171 markMCQQ.How much electricity in terms of Faraday is required for reduction of 2 mole Cr2O72− into Cr3+ in acidic medium? (A) 12 F (B) 3 F (C) 6 F (D) 9 F
›Reveal solutionSolution
6e− per Cr2O72− ⇒ 2 mol require 2×6=12 F.
Concept. In acidic medium each Cr goes from +6 to +3 (gain 3 e⁻); two Cr per dichromate ⇒ 6 e⁻: …
- GUJCET 2021Set 151 markMCQQ.Which products are obtained during electrolysis of aqueous solution of sodium chloride? (A) NaOH,O2 and H2 (B) NaOH,Na and H2 (C) NaOH,Cl2 and H2 (D) Na,Cl2 and H2
›Reveal solutionSolution
Aqueous NaCl electrolysis (chlor-alkali) → NaOH, Cl2, H2.
Concept: In the chlor-alkali process:
- Cathode: 2H2O+2e−→H2+2OH− (with Na+, gives NaOH). …
- GUJCET 2020Set 071 markMCQQ.On electrolysis of aqueous solution of a halide of a metal 'M' by passing 1.5 ampere current for 10 minutes deposits 0.2938 g of metal. If the atomic mass of the metal is 63 gm/mole, then what will be the formula of the metal halide? (A) MCl (B) MCl3 (C) MCl2 (D) MCl4
›Reveal solutionSolution
[!TLDR] The metal deposits in a 2-electron process (n≈2), so its formula is MCl2.
Concept
Faraday's law: moles of metal deposited =Q/(nF), where Q=It is the charge, n the number of electrons per metal ion, and F=96500 C/mol. Rearranging, n=(Q/F)/(moles of metal).
Solution
Q=It=1.5A×(10×60)s=900C.
Moles of electrons =96500900=9.33×10−3. …
- GUJCET 2019Set 131 markMCQQ.If one mole electrons is passed through the solutions of AlCl3, AgNO3 and MgSO4, in what ratio Al, Ag and Mg will be deposited at the electrodes? (A) 3 : 2 : 1 (B) 1 : 2 : 3 (C) 2 : 6 : 3 (D) 3 : 6 : 2
›Reveal solutionSolution
Moles deposited = (moles of electrons)/(charge on ion), giving Al : Ag : Mg = 1/3 : 1 : 1/2 = 2 : 6 : 3.
Concept — Faraday's law. The amount of a metal deposited is inversely proportional to the number of electrons its ion needs. Al³⁺ needs 3 e⁻, Ag⁺ needs 1 e⁻, Mg²⁺ needs 2 e⁻.
Steps. For 1 mole of electrons:
- nAl=31 …
- GUJCET 2015Set C1 markMCQQ.The resulting solution obtained at the end of electrolysis of concentrated aqueous solution of NaCl _____. (A) turns blue litmus into red (B) turns red litmus into blue (C) remains colourless with phenolphthalein (D) the colour of red or blue litmus does not change
›Reveal solutionSolution
[!TLDR]
Electrolysing concentrated aqueous NaCl leaves NaOH in the cell, a basic solution that turns red litmus blue; option (B).
Concept
In the chlor-alkali (electrolysis of concentrated NaCl) process:
- Cathode: 2H2O+2e−→H2+2OH− (H2 evolves).
- Anode: 2Cl−→Cl2+2e− (Cl2 evolves, from concentrated chloride).
The Na+ ions stay in solution with the newly formed OH−, so sodium hydroxide accumulates.
Solution …
- GUJCET 2015Set C1 markMCQQ.Two electrolytic cells containing molten solutions of Nickel chloride & Aluminium chloride are connected in series. If same amount of electric current is passed through them, what will be the weight of Nickel obtained when 18 gm of Aluminium is obtained? (Al - 27 gm/mole, Ni - 58.5 gm/mole−1) (A) 117 gm (B) 58.5 gm (C) 29.25 gm (D) 5.85 gm
›Reveal solutionSolution
[!TLDR]
Weight of nickel =58.5 g.
Concept
By Faraday's second law, when the same quantity of electricity flows through cells in series, the masses deposited are proportional to their equivalent masses (= molar mass ÷ electrons transferred).
Solution
- Al3++3e−→Al: equivalent mass =27/3=9.
- Ni2++2e−→Ni: equivalent mass =58.5/2=29.25. …
- GUJCET 2014Set A1 markMCQQ.Which of the following will give H2(g) at cathode and O2(g) at anode on electrolysis using platinum electrodes? (A) molten NaCl (B) concentrated aq. solution of NaCl (C) dilute aq. solution of NaCl (D) solid NaCl
›Reveal solutionSolution
[!TLDR] Dilute aqueous NaCl liberates H2 at the cathode and O2 at the anode, because water is discharged in preference to Na+ and (at low Cl−) to Cl−.
Concept
Electrode products in electrolysis depend on discharge potentials and ion concentration. In aqueous solution, Na+ is never discharged (water is reduced instead), so H2 appears at the cathode. At the anode, O2 (from water oxidation) and Cl2 (from Cl−) compete; a low Cl− concentration favours O2, while concentrated Cl− (overpotential effect) favours Cl2.
Solution …
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