Q.Explain how rusting of iron is envisaged as setting up of an electrochemical cell.
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Standard Electrode Potentials
Standard Electrode Potentials: A Number for "How Badly It Wants Electrons"
Dip a zinc rod into a zinc-salt solution and a tiny tug-of-war begins at the surface:
metal atoms tend to dissolve as ions (leaving electrons behind on the rod) while ions
from the solution tend to deposit as metal (consuming electrons). The rod ends up with
a characteristic electrical potential relative to the solution — the electrode potential. It is a direct measure of the tendency of that redox couple to gain or
lose electrons.
The Core Idea
Different couples pull electrons with very different strengths. Copper's ion grabs
them readily; zinc's barely wants them. Put a number on each couple and you can
predict, before mixing anything, who will oxidise whom.
Two conventions make the numbers comparable:
- Standard conditions. Every species at unit concentration (1 M), any gas at 1 atm, temperature 298 K. The potential measured then is the standard electrode potential, written E⊖.
- A common zero. Potentials can only be measured as differences, so one electrode is defined as the reference: the standard hydrogen electrode (SHE), 2H++2e−→H2, is fixed at exactly 0.00 V. Every E⊖ is the voltage of a couple measured against it.
By convention the values are tabulated for the reduction direction:
Oxidised form+ne−→Reduced formE⊖ (in volts, at 298 K)
Reading the Table
The standard-potential table (Table 7.1 in the Class 11 chapter) runs from
F2/F− at +2.87 V down to Li+/Li at −3.05 V.
Two rules unlock it:
- More positive E⊖ → stronger oxidising agent (the oxidised form is hungrier for electrons). F₂ tops the table; that is why fluorine oxidises almost everything.
- More negative E⊖ → stronger reducing agent (the reduced form gives electrons up most easily). Li, K, Ca, Na at the bottom are the great electron donors. A negative E⊖ means the couple is a stronger reducing agent than the H⁺/H₂ couple; a positive one, weaker.
Predicting Whether a Reaction Goes
For any proposed redox reaction, the species being reduced acts as the cathode couple
and the species being oxidised as the anode couple:
Ecell⊖=Ecathode⊖−Eanode⊖
A positive Ecell⊖ means the reaction is feasible
(spontaneous) under standard conditions; a negative one means the reverse reaction
is the spontaneous direction.
Worked feel: can Fe³⁺ oxidise iodide? E⊖(Fe3+/Fe2+)=+0.77 V is above E⊖(I2/I−)=+0.54 V, so
Ecell⊖=+0.23 V — yes. Can silver metal reduce Fe³⁺?
0.77−0.80=−0.03 V — no.
This is also the logic of the activity series: a metal displaces, from solution, …
Why this formula?
Galvanic Corrosion: Why the Key Formulas Hold
Galvanic corrosion occurs when two dissimilar metals are electrically connected in the presence of an electrolyte. The key formula that governs this is the mixed potential theory, which leads to the galvanic current and corrosion rate expressions.
Let's build the reasoning step-by-step.
1. The Core Idea: Two Electrodes, One Circuit
When metals M₁ (more active, e.g., zinc) and M₂ (more noble, e.g., copper) are connected:
- M₁ acts as the anode — it oxidizes (corrodes):
M1→M1n++ne−
- M₂ acts as the cathode — it reduces something (e.g., oxygen or H⁺):
O2+2H2O+4e−→4OH−(in neutral/alkaline)
or
2H++2e−→H2(in acidic)
The two metals are electrically connected (via a wire or direct contact), and the electrolyte completes the circuit. Electrons flow from M₁ to M₂.
2. The Mixed Potential: Why It Exists
Each metal, when alone in the electrolyte, has its own open-circuit potential (OCP) — the equilibrium potential for its half-reaction. For M₁, it's Ecorr,1; for M₂, it's Ecorr,2.
When connected, the system cannot stay at two different potentials. The entire metal couple must reach a single potential — the mixed potential Emix.
- Emix lies between Ecorr,1 and Ecorr,2.
- At Emix, the total anodic current from M₁ equals the total cathodic current from M₂ (charge conservation):
Ianode=Icathode
This is the fundamental equation of galvanic corrosion.
3. Deriving the Galvanic Current
Assume each electrode follows Butler-Volmer kinetics (for activation-controlled reactions). For the anode (M₁), the anodic current density ia at potential E is:
ia=i0,1exp(RTαaF(E−E0,1))
For the cathode (M₂), the cathodic current density ic is:
ic=i0,2exp(−RTαcF(E−E0,2))
Where:
- i0,1,i0,2 = exchange current densities
- αa,αc = transfer coefficients (typically ~0.5)
- F = Faraday constant
- R = gas constant
- T = temperature
- E0,1,E0,2 = standard reduction potentials
At the mixed potential Emix:
Igalvanic=A1⋅ia(Emix)=A2⋅ic(Emix)
Where A1 and A2 are the surface areas of the anode and cathode.
Why this holds: The net current from the anode must exactly balance the net current consumed at the cathode — otherwise, charge would accumulate, which is impossible in a steady-state circuit.
4. The Corrosion Rate Formula
The corrosion rate (mass loss per time) of the anode is given by Faraday's law:
Corrosion rate=n⋅F⋅ρIgalvanic⋅M
Where:
- M = molar mass of the anode metal
- n = number of electrons transferred per atom
- ρ = density of the metal
- F = Faraday constant (96,485 C/mol)
Why this holds: Each mole of metal oxidized releases n moles of electrons. The total charge passed Q=Igalvanic⋅t corresponds to moles of metal lost:
moles lost=nFQ=nFIgalvanic⋅t
Multiply by M/ρ to get volume or thickness loss.
5. The Area Effect: Why It Matters
From the mixed potential equation:
A1⋅ia(Emix)=A2⋅ic(Emix)
If the cathode area A2 is large relative to the anode area A1, then ia(Emix) must be large to balance the current. This means:
- Small anode + large cathode → severe galvanic corrosion (high current density on the anode). …
Rusting is best understood as a tiny short-circuited galvanic (electrochemical) cell set up on the iron surface: differences in oxygen access and impurities create separate anodic and cathodic regions on the same piece of metal, linked by electron flow through the iron and ion flow through a thin moisture film.
Step 1: Anodic spot (oxidation)
At an anodic spot the iron is oxidised and passes into solution as ferrous ions:
2Fe(s)⟶2Fe2+(aq)+4e−E(Fe2+/Fe)∘=−0.44 V
Step 2: Cathodic spot (reduction)
The electrons travel through the metal to a cathodic spot, where oxygen is reduced in the presence of H+ (available from H2CO3 formed when atmospheric CO2 dissolves in the moisture film):
O2(g)+4H+(aq)+4e−⟶2H2O(l)E(H+∣O2∣H2O)∘=1.23 V
Step 3: Overall cell reaction and rust
2Fe(s)+O2(g)+4H+(aq)⟶2Fe2+(aq)+2H2O(l)Ecell∘=1.67 V …
Rusting of iron is an electrochemical process in which the iron surface behaves as a short-circuited galvanic cell: at an anodic spot iron is oxidised (2Fe→2Fe2++4e−, E∘=−0.44 V) and at a cathodic spot oxygen is reduced in the presence of H+ (O2+4H++4e−→2H2O, E∘=1.23 V), giving Ecell∘=1.67 V. The Fe2+ is finally oxidised to rust, hydrated ferric oxide Fe2O3⋅xH2O.
The Core Idea: Why Rusting is Electrochemical
When you see a rusty iron gate, you are really looking at the result of a tiny, invisible battery. Iron does not simply "burn" in air — corrosion of iron is a redox process that separates into two half-reactions occurring at different spots on the same metal surface. This spatial separation of oxidation and reduction is the hallmark of an electrochemical cell.
The key point: a piece of iron is never perfectly uniform. It carries impurities, and even on pure iron different areas have different access to oxygen and moisture. These differences make some spots anodic and others cathodic, turning the iron surface into a short-circuited galvanic cell.
Step-by-Step Breakdown
1. The Anode (Oxidation Spot)
At an anodic spot — typically a strained region, an impurity site, or an area with poorer oxygen access — iron atoms lose electrons and go into the surrounding moisture as ferrous ions:
2Fe(s)⟶2Fe2+(aq)+4e−E(Fe2+/Fe)∘=−0.44 V
This is oxidation. The electrons released travel through the iron metal itself to a cathodic spot.
A common mistake is to think iron is oxidised directly to Fe3+. The first electrochemical step forms Fe2+; the Fe3+ (rust) appears only later, through further oxidation by atmospheric oxygen.
2. The Cathode (Reduction Spot)
At a cathodic spot — usually a region with better oxygen access — the electrons from the anode are consumed. Oxygen is reduced in the presence of H+:
O2(g)+4H+(aq)+4e−⟶2H2O(l)E(H+∣O2∣H2O)∘=1.23 V
Where do the H+ ions come from? They are believed to be available from carbonic acid (H2CO3) formed when atmospheric CO2 dissolves into the water film; H+ may also come from other acidic oxides dissolving from the atmosphere. This is why rusting is faster in moist, polluted, and CO2-rich air.
Under strongly alkaline or oxygen-rich neutral conditions the oxygen-reduction step can instead be written as O2+2H2O+4e−→4OH−. Both forms are legitimate representations of oxygen reduction, but for the atmospheric rusting discussed here the acidic form (with H+ from dissolved CO2) is the one used — it is what gives the standard Ecell∘=1.67 V below.
3. The Overall Cell Reaction
Adding the anode and cathode half-reactions (electrons already balance, 4 each):
2Fe(s)+O2(g)+4H+(aq)⟶2Fe2+(aq)+2H2O(l)Ecell∘=1.67 V
The cell potential follows directly from the two electrode values:
Ecell∘=Ecathode∘−Eanode∘=1.23−(−0.44)=1.67 V
A large positive Ecell∘ confirms the process is strongly spontaneous — iron rusts readily.
4. Formation of Rust (The Final Product)
The ferrous ions are further oxidised by atmospheric oxygen to ferric ions, which precipitate as rust — hydrated ferric oxide:
2Fe2+(aq)+2H2O(l)+21O2(g)⟶Fe2O3(s)+4H+(aq)
giving rust as Fe2O3⋅xH2O
Notice the H+ regenerated here feeds back into the cathodic reaction, so rusting keeps propagating.
The electrochemical cell of rusting:
Anode (oxidation): 2Fe→2Fe2++4e−, E∘=−0.44 V
Cathode (reduction): O2+4H++4e−→2H2O, E∘=1.23 V
…
Method: Electrochemical Cell Model of Corrosion
This method explains rusting by treating the iron surface as a short-circuited electrochemical cell with distinct anodic and cathodic spots.
Step 1: Identify the Anode (Oxidation Spot)
- At a scratch, strained region, or impurity on the iron surface, iron atoms lose electrons:
2Fe(s)⟶2Fe2+(aq)+4e−E(Fe2+/Fe)∘=−0.44 V
- This is the anodic half-reaction (oxidation). The iron dissolves into the moisture film.
Step 2: Identify the Cathode (Reduction Spot)
- At another region with better oxygen access, the electrons that travelled through the metal reduce oxygen in the presence of H+:
O2(g)+4H+(aq)+4e−⟶2H2O(l)E(H+∣O2∣H2O)∘=1.23 V
- The H+ is available from H2CO3 formed when atmospheric CO2 dissolves in the water film (and from other dissolved acidic oxides).
Step 3: Complete the Cell Circuit
- Electron flow: electrons move through the iron metal from the anodic spot to the cathodic spot.
- Ion flow: ions move through the water film (electrolyte) — Fe2+ from the anode and the products of reduction from the cathode.
Step 4: Write the Overall Cell Reaction
Adding the two half-reactions (4 electrons each):
2Fe(s)+O2(g)+4H+(aq)⟶2Fe2+(aq)+2H2O(l)
Step 5: Formation of Rust …
Common Mistakes: Rusting of Iron as an Electrochemical Cell
Mistake 1: Describing Rusting as a Simple, Direct Reaction With Oxygen
The error: Students write "iron reacts directly with oxygen to form rust" (4Fe+3O2→2Fe2O3) without mentioning any electrochemical mechanism.
Why it's wrong: The question asks you to explain rusting AS an electrochemical cell. A direct combustion-style equation misses the point: oxidation and reduction happen at physically separate spots on the iron surface, linked by electron flow through the metal and ion flow through a moisture film.
How to avoid: Always identify an anodic spot (where Fe is oxidised) and a cathodic spot (where O2 is reduced) — never lump them into one combined equation without explaining the two-spot mechanism.
Mistake 2: Writing Fe -> Fe(III) + 3e- as the First Oxidation Step
The error: Students jump straight to ferric ion (Fe3+) formation at the anode.
Why it's wrong: The initial oxidation at the anodic spot always produces Fe2+ first: 2Fe(s)→2Fe2+(aq)+4e−. Fe3+ appears only later, when the Fe2+ is further oxidised to rust by atmospheric oxygen.
How to avoid: Always write the anode half-reaction as forming Fe2+, and show the further oxidation to rust (Fe2O3⋅xH2O) as a separate, later step.
Mistake 3: Forgetting the Role of the Moisture Film as the Electrolyte
The error: Students describe electron flow through the iron but never mention what plays the role of the electrolyte, or what carries ions between the anodic and cathodic spots.
Why it's wrong: Without an electrolyte the circuit is incomplete. A thin film of moisture (containing dissolved CO2, salts, or acidic pollutants) carries the ions between the spots and completes the electrochemical cell.
How to avoid: Explicitly state "the thin film of water on the iron surface acts as the electrolyte," and note that dissolved salts and acidic oxides speed up rusting by increasing conductivity and supplying H+.
Mistake 4: Writing the Cathode Reaction Without H+ (or Not Knowing Its Source)
The error: Students write only "oxygen is reduced" with no equation, or drop the H+ and cannot say where it comes from — some even leave the cathode reaction unbalanced.
Why it's wrong: For the atmospheric rusting described here, the standard cathodic half-reaction is O2(g)+4H+(aq)+4e−→2H2O(l), E∘=1.23 V. The H+ is available from H2CO3 formed when atmospheric CO2 dissolves in the moisture film (and from other dissolved acidic oxides). Omitting the H+ or its source leaves the mechanism — and the cell potential Ecell∘=1.67 V — incomplete.
How to avoid: Write the full balanced cathode reaction O2+4H++4e−→2H2O and state that the H+ comes from dissolved CO2 (H2CO3). (In strongly alkaline/neutral aerated conditions one may instead write O2+2H2O+4e−→4OH−, but the acidic form is the one used for ordinary rusting and matches the standard Ecell∘.)
Mistake 5: Not Explaining Why This Counts as a "Cell" …
Showing the 12 most recent of 16 on this concept.
- CBSE 2026Set 56/3/11 markMCQQ.On electrolysis of very dilute aqueous solution of NaCl using platinum electrodes : (A) H2 gas is evolved at anode. (B) Na is produced at cathode. (C) O2 gas is evolved at anode. (D) H2 gas is evolved at cathode.
›Reveal solutionSolution
In very dilute aqueous NaCl with inert Pt electrodes, water’s reduction to H2 at the cathode and water’s oxidation to O2 at the anode outcompete the NaCl reactions. So H2 is produced at the cathode and O2 at the anode — making option (C) and (D) correct.
Why standard electrode potentials decide the outcome
Electrolysis is a battle of competing half-reactions. At each electrode, the species that is easier to oxidise (at the anode) or easier to reduce (at the cathode) will react first. “Easier” means having a more positive reduction potential for reduction, or a more negative reduction potential for oxidation (equivalently, a more positive oxidation potential).
For a very dilute aqueous solution of NaCl, the possible species are:
- Cathode (reduction): Na+ ions and H2O molecules.
- Anode (oxidation): Cl− ions and H2O molecules.
We compare their standard reduction potentials (at 298 K, 1 M concentration, 1 atm pressure). But remember: concentration matters. In very dilute NaCl, [Cl−] is tiny, which shifts the actual potential of the chlorine half-reaction significantly.
Step-by-step reasoning
1. What happens at the cathode?
Two reduction half-reactions compete:
Na++e−2H2O+2e−→Na(s)E∘=−2.71 V→H2(g)+2OH−E∘=−0.83 V
The reduction of water to hydrogen gas has a much less negative (i.e., more positive) standard potential. Even though the actual potential for water reduction depends slightly on pH (here neutral to slightly basic), it remains far above −2.71 V. So water is reduced preferentially.
Watch outA common mistake is to think that because Na+ is present, sodium metal will plate out. But sodium’s reduction potential is so negative that water (even in neutral solution) is reduced first. Sodium metal would instantly react with water anyway — it’s never produced in aqueous electrolysis.
Result at cathode: H2 gas is evolved. This matches option (D).
2. What happens at the anode?
Two oxidation half-reactions compete (written as reductions for comparison):
Cl2(g)+2e−O2(g)+4H++4e−→2Cl−E∘=+1.36 V→2H2OE∘=+1.23 V …
- CBSE 2026Set 56/2/11 markMCQQ.Consider the following reaction : Zn(s)+Ag2O(s)+H2O(l)→Zn2+(aq)+2Ag(s)+2OH−(aq) Given : EAg+/Ago=0.80 V, EZn2+/Zno=−0.76 V, 1F=96500 C mol−1 ΔrGo for the above reaction is : (A) −301.080 kJ mol−1 (B) +310.080 kJ mol−1 (C) −326.070 kJ mol−1 (D) −375.060 kJ mol−1
›Reveal solutionSolution
Zinc is oxidised and silver is reduced, giving Ecello=0.80−(−0.76)=1.56 V with n=2. Then ΔrGo=−nFEcello=−301.080 kJ mol−1, which is option (A).
The standard Gibbs energy of a cell reaction is linked to its standard cell potential by
ΔrGo=−nFEcello
so we first find Ecello, then n, and finally ΔrGo.
1. Identify the electrodes. Zinc is oxidised (anode) and silver is reduced (cathode):
Anode:Zn→Zn2++2e−
Cathode:Ag2O+H2O+2e−→2Ag+2OH−
2. Standard cell potential. Using the given reduction potentials,
Ecello=Ecathodeo−Eanodeo=0.80−(−0.76)=1.56 V
3. Electrons transferred. Each half-reaction involves 2 electrons, so n=2. …
- CBSE 2025Set D1 markMCQQ.The electromotive force of the following cell is: Zn | Zn2+ (1M) || Fe2+ (1M) | Fe, given E°Zn2+|Zn = -0.76 V, E°Fe2+|Fe = -0.44 V(a) 1.2 V(b) 0.32 V(c) -1.2 V(d) -0.32 V
›Reveal solutionSolution
E(cell) = E(cathode) - E(anode) = -0.44 - (-0.76) = +0.32 V.
In the cell notation Zn | Zn2+ || Fe2+ | Fe, zinc is the anode (oxidation, written left) and iron is the cathode (reduction, written right). The standard cell EMF is:
E(cell) = E(cathode) - E(anode)
E(cell) = E(Fe2+/Fe) - E(Zn2+/Zn)
E(cell) = (-0.44) - (-0.76) …
- CBSE 2025Set A1 markQ.Write True or False: The cell potential is the addition of the electrode potentials (reduction potentials) of the cathode and anode.
›Reveal solutionSolution
Cell potential is obtained by subtracting the anode's reduction potential from the cathode's, not by adding the two reduction potentials.
The standard cell potential is defined as:
Ecell∘=Ecathode(reduction)∘−Eanode(reduction)∘
If both electrode potentials are taken as reduction potentials (as the statement specifies), the correct operation is a subtraction (cathode minus anode), not an addition. The 'addition' phrasing is only valid if the anode's contribution is expressed as an oxidation potential (= −reduction potential): then …
- CBSE 2025Set ANNUAL1 markQ.Answer in one word/sentence: Given the standard electrode potentials, arrange these metals in their increasing order of reducting power: K+/K = -2.93 V, Ag+/Ag = 0.80 V, Hg2+/Hg = 0.79 V, Mg2+/Mg = -2.37 V.
›Reveal solutionSolution
Reducing power increases as the standard electrode (reduction) potential becomes more negative, so we simply rank the four E° values from most positive to most negative.
Given standard reduction potentials:
K+/K=−2.93 V,Mg2+/Mg=−2.37 V,Hg2+/Hg=+0.79 V,Ag+/Ag=+0.80 V
A more negative (or less positive) standard reduction potential means the metal has a greater tendency to lose electrons (be oxidised) — i.e. it is a stronger reducing agent. Conversely, a metal with a highly positive reduction potential prefers to stay reduced (gain electrons), making it a poor reducing agent (like Ag, a "noble" metal).
…
- CBSE 2025Set ANNUAL1 markQ.Write two applications of electrochemical series.
›Reveal solutionSolution
Electrochemical series: predicts reaction feasibility and metal-displacement reactivity.
The electrochemical series arranges elements/ions in order of their standard reduction potentials (E°). Two common applications:
- Predicting feasibility of a redox reaction: a reaction is spontaneous if the species with the higher (more positive) reduction potential is reduced while the species with the lower (more negative) reduction potential is oxidized, i.e. E°cell=E°cathode−E°anode>0. …
- CBSE 2024Set 56/3/11 markMCQQ.During the electrolysis of aqueous NaCl, the cathodic reaction is : (A) Oxidation of Cl− ion (B) Reduction of Na+ ion (C) Oxidation of H2O (D) Reduction of H2O
›Reveal solutionSolution
In aqueous NaCl electrolysis, the cathode is where reduction occurs. The competing reductions are Na+ and H2O; water has a much less negative reduction potential, so it is reduced instead of sodium. The correct answer is (D) Reduction of H2O.
The key to this question lies in understanding Standard Electrode Potentials — the numerical measure of a species’ tendency to gain electrons (be reduced). In electrolysis, the cathode is the negative electrode where reduction happens. When you have an aqueous solution, you must consider all possible reducible species, not just the obvious cation from the salt.
For aqueous NaCl, the solution contains:
- Na+ ions (from the salt)
- H2O molecules (the solvent)
- Cl− ions (from the salt — but these are oxidised at the anode, not reduced at the cathode)
At the cathode, two reduction reactions compete:
-
Reduction of Na+:
Na++e−→Na(s)
Standard reduction potential: E∘=−2.71 V
-
Reduction of water:
2H2O+2e−→H2(g)+2OH−
Standard reduction potential: E∘=−0.83 V
Watch outA common mistake is to assume that because Na+ is the cation, it must be reduced at the cathode. But the more positive (or less negative) the reduction potential, the easier the reduction. Here, water’s potential (−0.83 V) is far less negative than sodium’s (−2.71 V), meaning water is much more readily reduced.
Now, let’s work through the reasoning step by step.
-
Identify the cathode process.
The cathode is the electrode where reduction occurs — gain of electrons. So we look for which species can accept electrons.
-
List all reducible species in the solution.
In aqueous NaCl: Na+ ions and H2O molecules. (The Cl− ions are already in their lowest oxidation state for a halide; they cannot be reduced further under these conditions — they are oxidised at the anode.)
-
Compare their reduction potentials.
- Na++e−→Na: E∘=−2.71 V
- 2H2O+2e−→H2+2OH−: E∘=−0.83 V
The more positive (or less negative) the potential, the stronger the oxidising agent — i.e., the more likely it is to be reduced. Since −0.83>−2.71, water is a much stronger oxidising agent than Na+ in this system. …
- CBSE 2024Set ANNUAL1 markQ.In which electrode of a Galvanic cell, oxidation reaction takes place?
›Reveal solutionSolution
The anode of a galvanic cell is where oxidation (electron loss) occurs.
A Galvanic (voltaic) cell converts the chemical energy of a spontaneous redox reaction into electrical energy, splitting the reaction into two half-cells. The electrode at which oxidation (loss of electrons) takes place is called the anode; in a galvanic cell this is the negative electrode. For example, in the Daniell cell, Zn(s)→Zn2+(aq)+2e− o …
- CBSE 2024Set ANNUAL1 markMCQQ.Emf of a cell with Nickel and Copper electrode will be (Given E0 Ni+2/Ni = -0.25 V, E0 Cu2+/Cu = +0.34 V)(a) -0.59 V(b) +0.59 V(c) +0.09 V(d) -0.09 V
›Reveal solutionSolution
The electrode with the higher (more positive) standard reduction potential acts as the cathode; the cell EMF is Ecathode - Eanode.
Given: E-degree(Ni2+/Ni) = -0.25 V, E-degree(Cu2+/Cu) = +0.34 V.
Since Cu2+/Cu has the higher reduction potential, copper is reduced (cathode) and nickel is oxidised (anode):
Anode (oxidation): Ni -> Ni2+ + 2e-
Cathode (reduction): Cu2+ + 2e- -> Cu
…
- CBSE 2023Set 56/1/11 markMCQQ.ΔG and Ecell∘ for a spontaneous reaction will be : (A) positive, negative (B) negative, negative (C) negative, positive (D) positive, positive
›Reveal solutionSolution
A spontaneous reaction releases free energy (ΔG<0) and generates a positive cell potential (Ecell∘>0); the answer is (C).
The connection between thermodynamics and electrochemistry rests on a beautiful relationship: the Gibbs free energy change tells us whether a reaction will proceed on its own, while the standard cell potential measures the driving force behind electron flow. For a reaction to be spontaneous, it must release free energy to do useful work—including pushing electrons through a circuit.
The fundamental bridge between these quantities is:
ΔG∘=−nFEcell∘
where n is the number of moles of electrons transferred, F is Faraday's constant (96,485C/mol), and Ecell∘ is the standard cell potential.
The negative sign in this equation is the key. It tells us that a positive cell potential (electrons flowing spontaneously from anode to cathode, releasing energy) corresponds to a negative Gibbs free energy change (energy released, reaction spontaneous). Think of it this way: when a battery drives current through a device, it's doing work on the surroundings, which means the battery's chemical reaction is losing free energy—hence ΔG<0.
Now let's apply this to the question:
-
What does spontaneity require thermodynamically?
A spontaneous process proceeds without external intervention and releases free energy. The criterion is ΔG<0 (negative). This is the defining condition—if ΔG were positive, we'd need to supply energy to make the reaction go.
-
What does the equation tell us about Ecell∘?
Rearranging: Ecell∘=−nFΔG∘. Since n and F are always positive, and we've established that ΔG∘<0 for a spontaneous reaction, the negative sign in front flips the inequality: Ecell∘>0 (positive).
-
Physical interpretation
A positive standard cell potential means the cathode (reduction site) has a higher reduction potential than the anode (oxidation site). Electrons naturally flow "downhill" in potential, from lower to higher reduction potential, generating voltage. This is exactly what happens in a galvanic (voltaic) cell—the spontaneous reaction produces electrical energy. …
-
- CBSE 2023Set 56/3/11 markMCQQ.Assertion (A): Electrolysis of aqueous solution of NaCl gives chlorine gas at anode instead of oxygen gas. Reason (R): Formation of oxygen gas at anode requires overpotential. (A) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A). (B) Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of the Assertion (A). (C) Assertion (A) is true, but Reason (R) is false. (D) Assertion (A) is false, but Reason (R) is true.
›Reveal solutionSolution
In the electrolysis of aqueous NaCl, chlorine is produced at the anode instead of oxygen because the overpotential for oxygen evolution makes the actual potential needed for oxygen formation higher than that for chlorine, even though the standard potential for oxygen is lower. Both Assertion and Reason are true, and the Reason correctly explains the Assertion — so the answer is (A).
Why this question is about real-world electrochemistry
Standard electrode potentials tell you which reaction is thermodynamically favoured. But electrolysis happens under kinetic conditions. The key twist here: oxygen evolution at an inert anode (like platinum or graphite) has a large overpotential — an extra voltage needed to overcome the activation barrier. Chlorine evolution, on the other hand, has a much smaller overpotential. So the reaction that actually occurs at the anode is not the one with the lower standard potential, but the one that requires the lower actual voltage (standard potential + overpotential).
Let’s see the numbers.
1. What are the possible anode reactions?
In aqueous NaCl, the solution contains these ions:
Na+, Cl−, H+ (from water), and OH− (from water).
At the anode, oxidation happens. The two candidates are:
- Oxidation of chloride ions:
2Cl−→Cl2+2e−E∘=+1.36 V
- Oxidation of water (to oxygen):
2H2O→O2+4H++4e−E∘=+1.23 V
NoteStandard potentials are given as reduction potentials. For oxidation, we reverse the sign. But when comparing which oxidation is easier, we compare the actual potentials needed — the more negative the oxidation potential (or the lower the reduction potential), the easier it is to oxidise. Here, water oxidation has E∘=+1.23 V (reduction), so its oxidation potential is −1.23 V. Chloride oxidation has E∘=+1.36 V (reduction), so its oxidation potential is −1.36 V. Since −1.23>−1.36, water oxidation is thermodynamically easier — it should occur first.
So why doesn’t it?
2. The role of overpotential
Overpotential (η) is the extra voltage beyond the thermodynamic value required to drive a reaction at a noticeable rate. For oxygen evolution on common anode materials (Pt, graphite), η is substantial — typically around 0.4–0.6 V. For chlorine evolution on the same materials, η is very small (often <0.1 V).
So the actual potential needed for each reaction is:
- For oxygen:
Eactual(O2)=1.23 V+ηO2≈1.23+0.5=1.73 V
- For chlorine:
Eactual(Cl2)=1.36 V+ηCl2≈1.36+0.05=1.41 V
Now compare: chlorine requires a lower actual voltage (1.41 V) than oxygen (1.73 V). So chlorine is produced preferentially. …
- CBSE 2023Set ANNUAL1 markMCQQ.When concentration of Zn2+ and Cu2+ ions is unity (1 mol dm-3), then electrical potential of Daniell cell will be -(a) 0.00 V(b) 1.10 V(c) 1.35 V(d) 2.00 V
›Reveal solutionSolution
A Daniell cell is Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s); its EMF is the difference of the two standard reduction potentials, and at unit concentration this IS the standard cell potential.
The Daniell cell has the cell reaction Zn(s) + Cu2+(aq) -> Zn2+(aq) + Cu(s), with Zn as the anode (oxidation) and Cu as the cathode (reduction).
Standard reduction potentials: E-standard(Cu2+/Cu) = +0.34 V, E-standard(Zn2+/Zn) = -0.76 V.
…
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