Q.Consult the table of standard electrode potentials and suggest three substances that can oxidise ferrous ions under suitable conditions.
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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). …
The key idea is that a substance can oxidise Fe2+ to Fe3+ if its standard reduction potential is greater than E∘(Fe3+/Fe2+)=+0.77 V.
- The half-reaction for oxidation is: Fe2+→Fe3++e− (reverse of the reduction).
- Any oxidising agent with E∘>+0.77 V will spontaneously accept electrons from Fe2+.
- From the standard potential series, three common examples are:
- Cl2: Cl2+2e−→2Cl−, E∘=+1.36 V
- Br2: Br2+2e−→2Br−, E∘=+1.09 V …
The key idea is that a substance can oxidise FeX2+ to FeX3+ if its standard reduction potential is greater than +0.77 V (the E∘ for FeX3+/FeX2+). Three such oxidising agents are FX2, ClX2, and OX3.
Why Standard Electrode Potentials Decide the Reaction
Oxidation is the loss of electrons. For FeX2+ to be oxidised to FeX3+, it must give away an electron. That electron must be accepted by some other species — the oxidising agent. The tendency of a species to accept electrons is measured by its standard reduction potential (E∘). The more positive the E∘, the stronger the oxidising agent.
The half-reaction for ferrous oxidation is:
FeX3++eX−FeX2+E∘=+0.77 V
This value tells us that FeX3+ has a moderate tendency to get reduced back to FeX2+. To push the reaction in the opposite direction — to force FeX2+ to lose an electron — we need an oxidising agent that is even more eager to gain electrons. In other words, the oxidising agent's reduction potential must be greater than +0.77 V.
A species X can oxidise FeX2+ to FeX3+ if:
E∘(X/X−)>+0.77 V
Step-by-step selection
-
Recall the standard reduction potentials of common oxidising agents. From the standard table (at 25∘C, 1 atm, 1 M), we have:
- FX2+2eX−2FX−: E∘=+2.87 V
- OX3+2HX++2eX−OX2+HX2O: E∘=+2.07 V
- ClX2+2eX−2ClX−: E∘=+1.36 V
- MnOX4X−+8HX++5eX−MnX2++4HX2O: E∘=+1.51 V
- CrX2OX7X2−+14HX++6eX−2CrX3++7HX2O: E∘=+1.33 V
- BrX2+2eX−2BrX−: E∘=+1.09 V
- IX2+2eX−2IX−: E∘=+0.54 V
-
Compare each with +0.77 V. Any species with E∘>0.77 V can, in principle, oxidise FeX2+. Those with E∘<0.77 V (like IX2) cannot.
-
Select three distinct substances that are commonly available and clearly satisfy the condition. Good choices are:
- Fluorine gas (FX2): E∘=+2.87 V — the strongest oxidising agent known.
- Chlorine gas (ClX2): E∘=+1.36 V — a classic laboratory oxidiser.
- Ozone (OX3): E∘=+2.07 V — a powerful oxidant used in water treatment.
Other valid options include KMnOX4 (acidified), KX2CrX2OX7 (acidified), or BrX2, but the question asks for three substances, and the above are unambiguous. …
Method: Using Standard Electrode Potentials to Predict Redox Feasibility
Method name: The Ecell∘ Sign Rule (or Spontaneity Rule)
Concept behind the method
A substance can oxidise ferrous ions (Fe2+) if it can accept electrons from Fe2+, converting Fe2+ to Fe3+.
The half-reaction for oxidation of ferrous ions is:
Fe2+→Fe3++e−E∘=+0.77 V
For a reaction to be spontaneous (feasible), the overall cell potential must be positive:
Ecell∘=Ecathode∘−Eanode∘>0
Here, the anode (oxidation) is Fe2+→Fe3++e− with E∘=+0.77 V.
The cathode (reduction) is the substance that will accept electrons — its E∘ must be greater than +0.77 V.
Steps
-
Identify the half-reaction for the substance to be oxidised
- Here: Fe2+→Fe3++e−, E∘=+0.77 V
-
Recall the condition for a substance to act as an oxidising agent
- The oxidising agent (cathode) must have a higher reduction potential than the substance being oxidised (anode).
-
Consult the standard electrode potential table
- Look for half-reactions with E∘>+0.77 V.
-
Select three substances whose reduction potentials are greater than +0.77 V.
Three substances that can oxidise Fe2+
| Substance | Reduction half-reaction | E∘ (V) | …
Here are the common mistakes students make when tackling this exact type of question from Standard Electrode Potentials, along with clear strategies to avoid each.
Mistake 1: Confusing “Oxidise” with “Reduce”
- The error: Students think any substance with a higher reduction potential than Fe2+/Fe will oxidise Fe2+. They often pick metals like Zinc (E∘=−0.76 V) because “it’s more reactive.”
- Why it’s wrong: To oxidise Fe2+ (turn it into Fe3+), the oxidising agent must itself be reduced. This means the oxidising agent must have a higher reduction potential than the Fe3+/Fe2+ couple (+0.77 V). A lower potential means the substance is a reducing agent, not an oxidising agent.
- How to avoid: Always write the half-reaction for the species being oxidised:
Fe2+→Fe3++e−(E∘=+0.77 V)
Then, the oxidising agent must have a more positive E∘ than +0.77 V.
Mistake 2: Forgetting the Correct Half-Cell for Iron
- The error: Using the Fe2+/Fe couple (−0.44 V) instead of the Fe3+/Fe2+ couple (+0.77 V).
- Why it’s wrong: The question asks to oxidise ferrous ions (Fe2+) to ferric ions (Fe3+). The relevant half-reaction is:
Fe3++e−⇌Fe2+E∘=+0.77 V
The Fe2+/Fe couple is for reduction to metallic iron, which is a different process.
- How to avoid: Memorise the key couples for iron:
- Fe3+/Fe2+: +0.77 V (for oxidation of Fe2+)
- Fe2+/Fe: −0.44 V (for reduction to metal)
Mistake 3: Picking Substances with E∘ Exactly Equal to +0.77 V
- The error: Choosing I2/I− (+0.54 V) or Cu2+/Cu (+0.34 V) because they are “close” to +0.77 V.
- Why it’s wrong: For a spontaneous reaction, the oxidising agent must have E∘>+0.77 V. If E∘ is lower, the reaction is non-spontaneous under standard conditions. The reaction will not proceed.
- How to avoid: Use the spontaneity rule:
ΔG∘=−nFEcell∘
For a spontaneous reaction, Ecell∘>0. Here:
Ecell∘=Eoxidising agent∘−0.77 V
So you need Eoxidising agent∘>0.77 V.
Mistake 4: Not Checking the Table Carefully
- The error: Listing substances like Cl2 (+1.36 V) but forgetting that Cl2 is a gas and may not be “suitable” under all conditions (e.g., in solution, it can also oxidise water).
- Why it’s wrong: The question says “under suitable conditions.” While Cl2 works in principle, students often miss that MnO4− (+1.51 V) or Cr2O72− (+1.33 V) are more common lab oxidising agents for Fe2+.
- How to avoid: List three distinct substances from the table with E∘>+0.77 V. Good choices:
- Cl2 (+1.36 V)
- MnO4− in acid (+1.51 V)
- Cr2O72− in acid (+1.33 V) …
- Council of Higher Secondary Education, Manipur (Higher Secondary 1st Year) 2026Set ANNUAL1 markMCQQ.Assertion (A): In the displacement reaction M(s) + AgNO3(aq) → M(NO3)2 + 2Ag(s) the metal M acts as reductant. Reason (R): Reduction potential of metal M is lower than that of silver.(a) Both A and R are true and R is the correct explanation of A.(b) Both A and R are true but R is not the correct explanation of A.(c) A is true but R is false.(d) A is false but R is correct.
›Reveal solutionSolution
M reduces Ag+ to Ag by giving up electrons (acting as reductant) precisely because M has a lower reduction potential than silver — both A and R are true, and R explains A.
Assertion (A): In M(s)+2AgNO3(aq)→M(NO3)2(aq)+2Ag(s), metal M loses electrons (is oxidized, M→M2++2e−) while Ag+ gains electrons (is reduced, Ag++e−→Ag). A species that is itself oxidized while causing another to be reduced is the reducing agent (reductant). So A is TRUE.
…
- Council of Higher Secondary Education, Manipur (Higher Secondary 1st Year) 2023Set ANNUAL1 markQ.Why is standard hydrogen electrode called a reversible electrode?
›Reveal solutionSolution
The SHE is reversible because passing an infinitesimally small current in either direction simply reverses its electrode reaction without any large change in potential.
The standard hydrogen electrode consists of platinum foil (coated with platinum black) dipped in a 1 M solution of H+ ions, with hydrogen gas at 1 bar pressure and 298 K bubbled over it. Its electrode reaction is:
H+(aq) + e- <=> 1/2 H2(g)
When the SHE is connected as the cathode (in a cell where it undergoes reduction), H+ ions gain electrons to form H2 gas. When it is connected as the anode, H2 gas is oxidised at the electrode surface to give back H+ ions and electrons. Because passing only a vanishingly small (infinitesimal) current in either direction is enough to make the reaction go forward or backward, and the electrode returns to essentially the same equilibrium state, the process is thermodynamically reversible -- unlike an irreversible electrode where a finite current is needed and the potential changes sharply and permanently with the direction of current flow.
…
- Council of Higher Secondary Education, Manipur (Higher Secondary 1st Year) 2022Set ANNUAL1 markQ.The redox potential of four metals are given as : M1+/M1 = -2.93 V, M2^2+/M2 = -0.13 V, M3^1+/M3 = 0.34 V, and M4^2+/M4 = 0.80 V. Arrange the metals in increasing order of reactivity.
›Reveal solutionSolution
Reactivity of a metal (its tendency to lose electrons / get oxidized) increases as its standard reduction potential becomes more negative — rank the given potentials from most positive to most negative to get increasing reactivity.
The standard electrode (reduction) potential measures how readily a species gains electrons (is reduced). A metal with a highly positive reduction potential strongly prefers to stay in its reduced (metallic) form and resists losing electrons — such a metal is chemically unreactive (noble). A metal with a very negative reduction potential has little tendency to be reduced; instead it readily loses electrons (is oxidized) — such a metal is highly reactive.
Given values:
- M1⁺/M1 = −2.93 V (most negative → most reactive)
- M2²⁺/M2 = −0.13 V
- M3⁺/M3 = +0.34 V …
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