Q.Write down the electronic configuration of:
Concept understanding — Stability of Oxidation States
Stability of Oxidation States – From Intuition to Precision
Imagine you're holding a ball on a hill. If you place it exactly at the top, it's balanced — but the slightest push sends it rolling down. That's an unstable position. If you place it in a small dip on the hillside, it stays put even if nudged — that's stable. Oxidation states work the same way: some are like the hilltop (easily changed), others like the dip (hard to change).
The Core Intuition
An oxidation state is just a number we assign to an atom to track how many electrons it has gained or lost compared to its neutral state. But atoms don't "want" to stay in arbitrary oxidation states — they want to reach a configuration that minimises their energy.
Stability here means: how reluctant is that oxidation state to change under normal conditions? A stable oxidation state resists being oxidised further or reduced further. An unstable one readily changes into something else.
The Precise Statement
Stability of an oxidation state refers to the tendency of an element to maintain that particular oxidation state under given conditions (temperature, pH, presence of other reagents). A stable oxidation state is one that does not easily undergo redox reactions — it is neither easily oxidised nor easily reduced.
This depends on three key factors:
- Electronic configuration – Half-filled and fully-filled d or f subshells confer extra stability (e.g., Fe3+ with d5 is more stable than Fe2+ with d6 in some contexts).
- Inert pair effect – Heavier p-block elements (like Tl, Pb, Bi) show lower oxidation states (e.g., +1 for Tl) as more stable than higher ones (+3 for Tl), because the s-electrons become reluctant to participate.
- Disproportionation tendency – Some oxidation states are unstable because they spontaneously convert into two other states (e.g., Cu+ in aqueous solution gives Cu2+ and Cu).
Stability is relative — it depends on the environment. Mn2+ is stable in acidic solution but easily oxidised in alkaline medium. Always specify conditions when discussing stability.
Examples That Make It Concrete
Transition metals – Cr3+ (d3) and Mn2+ (d5) are exceptionally stable because half-filled/half-filled-like configurations have low energy. Cr2+ (d4) is easily oxidised to Cr3+ — it's unstable.
p-block elements – Pb2+ is stable, Pb4+ is a strong oxidising agent (unstable). Sn2+ is a reducing agent (easily oxidised to Sn4+), so Sn4+ is more stable for tin.
Common pattern – For most elements, the most common oxidation state is the most stable one under standard conditions. But "most common" isn't always "most stable" — e.g., Fe3+ is common but Fe2+ is more stable in acidic solution.
Do not confuse "stability" with "occurrence". Mn7+ (as MnO4−) is common in the lab but is a powerful oxidising agent — it is not stable in the sense of resisting change. It readily accepts electrons.
How to Think About It in Exams
When asked "Explain the stability of oxidation states of [element]", follow this mental checklist:
- Write the electronic configuration of the atom.
- Write configurations for each possible oxidation state.
- Look for half-filled, fully-filled, or inert pair effects.
- Check if the state can disproportionate (common for +1 states of Cu, Au, and +3 states of Mn).
- Mention the medium (acidic/alkaline) if relevant.
For d-block elements, remember: d0, d5, and d10 are especially stable. For p-block, the inert pair effect makes lower oxidation states more stable as you go down the group.
The Bottom Line
Stability of an oxidation state is a measure of how strongly an atom holds onto that oxidation number — how hard it is to push it up or down. It's determined by electronic structure, the element's position in the periodic table, and the chemical environment. Master this, and you'll predict redox behaviour without memorising every reaction.
Stability of oxidation states among transition and inner-transition elements is discussed in the NCERT/CBSE Class 12 Chemistry chapter on d- and f-Block Elements, and ‘stability of oxidation states in transition elements’ is a frequently searched important-question topic for board exams, JEE Main and NEET. Predicting which oxidation state is most stable is a reasoning skill regularly tested in competitive-exam inorganic chemistry MCQs.
Why this formula?
Stability of Oxidation States: Why It Works
This concept explains why certain oxidation states of an element are more stable than others — and why some states are never observed at all.
The Core Idea: Energy Minimisation
An oxidation state is stable when the total energy of the system is at a minimum. This depends on three competing factors:
- Ionisation energy (energy needed to remove electrons)
- Lattice energy (for ionic compounds) or bond energy (for covalent compounds)
- Electronic configuration (half-filled / fully-filled subshells)
There is no single formula for stability — instead, we use trends and principles that act as "formulae" for prediction.
Key Principle 1: Inert Pair Effect (for p-block elements)
Why it holds:
For heavier elements (e.g., Tl, Pb, Bi), the 6s² electrons are held very tightly due to poor shielding and relativistic effects. They resist removal.
- Result: Lower oxidation state (e.g., +1 for Tl, +2 for Pb) becomes more stable than the higher state (+3, +4).
- Example: TlX3+ is a strong oxidising agent — it readily gains two electrons to become TlX+.
Derivation logic:
The energy cost to remove the 6s² electrons is greater than the energy gained by forming additional bonds or lattice. So the system stays in the lower state.
Key Principle 2: Half-Filled / Fully-Filled Subshell Stability
Why it holds:
A half-filled (d5, f7) or fully-filled (d10, f14) subshell has extra exchange energy and symmetry — making it unusually stable.
- Example: MnX2+ (d5) is more stable than MnX3+ (d4). FeX3+ (d5) is more stable than FeX2+ (d6).
Derivation logic:
The exchange energy (Hund's rule) is maximum for half-filled configurations. Removing an electron from a half-filled shell costs extra energy — so the half-filled state is favoured.
Key Principle 3: Lattice Energy / Hydration Energy Compensation
For transition metals, stability of a particular oxidation state in aqueous solution depends on:
ΔG∘=ΔHhydration∘−ΔHionisation∘
Why it holds:
- Higher oxidation states have higher ionisation energy (harder to remove electrons).
- But they also have higher hydration energy (smaller, more charged ions attract water more strongly).
- The balance determines which state is stable.
Example:
- CuX+ is unstable in water because its hydration energy is too low to compensate for the loss of the second electron.
- CuX2+ is stable in water.
Key Principle 4: Disproportionation
Some oxidation states are unstable and spontaneously convert to two other states:
2CuX+Cu+CuX2+
Why it holds:
The free energy change ΔG∘ for the reaction is negative. This happens when the intermediate oxidation state is less stable than the extremes.
Formula (for aqueous ions):
If Ereduction∘ for the higher state is more positive than for the lower state, disproportionation is spontaneous.
Summary Table: Why Each "Formula" Holds
| Principle | Why it works | Key exam example |
|---|---|---|
| Inert pair effect | 6s² electrons are too tightly bound | PbX2+ stable, PbX4+ oxidising |
| Half-filled stability | Extra exchange energy | MnX2+ > MnX3+ |
| Hydration vs ionisation | Energy balance in solution | CuX2+ stable, CuX+ not |
| Disproportionation | ΔG<0 for intermediate state | CuX+ in water |
Final Takeaway for Exams
Never memorise stability blindly. Always ask:
- Is the electronic configuration special? (half-filled / inert pair)
- Is the medium aqueous or solid? (hydration vs lattice)
- Does the element belong to a heavier group? (inert pair effect)
The "formula" is really a balance of energies — and the reasoning is what gets you marks.
Concept: Stability of Oxidation States — ions with half-filled, fully-filled, or empty d/f subshells are particularly stable.
Reasoning:
- Write the ground-state configuration of the neutral atom.
- Remove electrons from the outermost orbitals (ns before (n−1)d for transition metals; 6s before 4f for lanthanides/actinides).
- Adjust for stability: Cr3+ loses the 4s1 electron first, then two 3d electrons.
- Cr: [Ar]3d54s1 → remove 4s1 + two 3d → [Ar]3d3
- Pm: [Xe]4f56s2 → remove 6s2 + one 4f → [Xe]4f4
- Cu: [Ar]3d104s1 → remove 4s1 → [Ar]3d10
- Ce: [Xe]4f15d16s2 → remove 6s2 + 5d1 + one 4f → [Xe] (empty 4f)
- Co: [Ar]3d74s2 → remove 4s2 → [Ar]3d7
- Lu: [Xe]4f145d16s2 → remove 6s2 (2 e⁻, matching the +2 charge) → [Xe]4f145d1
- Mn: [Ar]3d54s2 → remove 4s2 → [Ar]3d5
- Th: [Rn]6d27s2 → remove 7s2 + 6d2 → [Rn]
✓Final answer
(i) [Ar]3d3 (ii) [Xe]4f4 (iii) [Ar]3d10 (iv) [Xe] (v) [Ar]3d7 (vi) [Xe]4f145d1 (vii) [Ar]3d5 (viii) [Rn]
The key idea is to first write the ground-state configuration of the neutral atom, then remove electrons from the outermost shells (highest n, then highest l within that n) to form the cation. The final configurations are: (i) [Ar]3d3,
(ii) [Xe]4f4,
(iii) [Ar]3d10,
(iv) [Xe]4f0,
(v) [Ar]3d7,
(vi) [Xe]4f145d1,
(vii) [Ar]3d5,
(viii) [Rn].
When writing electronic configurations for ions, the most common mistake is to remove electrons from the last filled subshell in the neutral atom. That is wrong. The correct rule: electrons are removed from the orbital with the highest principal quantum number n first. If two orbitals share the same n, remove from the one with the higher azimuthal quantum number l (i.e., p before s, d before p, etc.). This is because orbitals with higher n are farther from the nucleus and less tightly bound.
For transition metals and lanthanides/actinides, this means that the ns electrons (where n is the period number) are lost before the (n−1)d or (n−2)f electrons. Let’s apply this step by step.
1. Cr3+
Neutral Cr (Z=24) has configuration: [Ar]3d54s1.
Why 3d54s1 and not 3d44s2? Because a half-filled d subshell (d5) is extra stable — this is an exception you must remember.
To form Cr3+, remove 3 electrons. Start with the highest n: the 4s electron goes first. That gives [Ar]3d5. Then remove two more from the 3d subshell (since n=3 is now the highest). 3d5 minus 2 electrons = 3d3.
Do not remove 4s electrons last. Many students write [Ar]3d24s1 for Cr3+, which is incorrect. The 4s orbital is higher in energy than 3d once the atom is ionized.
Answer: [Ar]3d3
2. Pm3+
Promethium (Pm, Z=61) is a lanthanide. Neutral configuration: [Xe]4f56s2.
Lanthanides fill the 4f subshell after 6s. For Pm3+, remove 3 electrons. Highest n is 6: remove both 6s electrons first. Then remove one more from the 4f subshell (next highest n is 4). 4f5 minus 1 = 4f4.
Answer: [Xe]4f4
3. Cu+
Copper (Cu, Z=29) neutral: [Ar]3d104s1 (another exception — full d subshell is stable).
Remove 1 electron. Highest n is 4: remove the 4s electron. That leaves [Ar]3d10.
Cu+ has a completely filled d subshell (d10), which is very stable. This is why copper(I) compounds are common.
Answer: [Ar]3d10
4. Ce4+
Cerium (Ce, Z=58) neutral: [Xe]4f15d16s2 (NCERT Table 4.9's form; the alternative 4f26s2 is sometimes quoted in the literature).
Remove 4 electrons. First, remove both 6s electrons, then the 5d electron, then the single 4f electron. So the configuration is just the noble gas core [Xe].
Answer: [Xe]
5. Co2+
Cobalt (Co, Z=27) neutral: [Ar]3d74s2.
Remove 2 electrons. Highest n is 4: remove both 4s electrons. That leaves [Ar]3d7.
Answer: [Ar]3d7
6. Lu2+
Lutetium (Lu, Z=71) neutral: [Xe]4f145d16s2.
Remove 2 electrons. Highest n is 6: remove both 6s electrons. That leaves [Xe]4f145d1.
Lu is the last lanthanide; its 4f subshell is full (4f14). The 5d electron is present because after 4f14, the next electron goes into 5d (not 4f).
Answer: [Xe]4f145d1
7. Mn2+
Manganese (Mn, Z=25) neutral: [Ar]3d54s2.
Remove 2 electrons. Highest n is 4: remove both 4s electrons. That leaves [Ar]3d5.
Mn2+ has a half-filled d subshell (d5), which gives it extra stability. This is why manganese(II) is a common oxidation state.
Answer: [Ar]3d5
8. Th4+
Thorium (Th, Z=90) is an actinide. Neutral: [Rn]6d27s2.
Remove 4 electrons. Highest n is 7: remove both 7s electrons. Then remove two from 6d: 6d2 minus 2 = 6d0. So the configuration is just [Rn].
Answer: [Rn]
The configurations are: (i) [Ar]3d3,
(ii) [Xe]4f4,
(iii) [Ar]3d10,
(iv) [Xe],
(v) [Ar]3d7,
(vi) [Xe]4f145d1,
(vii) [Ar]3d5,
(viii) [Rn].
Method: Electronic Configuration Using the Aufbau Principle + Ionization Sequence
This method uses the Aufbau order (filling order: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p) and the rule that for ions, electrons are removed first from the outermost shell (highest n), not from the subshell that was filled last.
Steps
- Write the ground-state configuration of the neutral atom using the Aufbau order.
- Remove electrons equal to the positive charge, starting from the highest principal quantum number (n) shell.
- Write the final configuration in order of increasing n (and within same n, increasing ℓ).
Solutions
(i) Cr3+
- Neutral Cr (Z = 24): [Ar]3d54s1 (Exception: half-filled d-subshell stability)
- Remove 3 electrons: first from 4s (1 e⁻), then from 3d (2 e⁻)
- Cr3+: [Ar]3d3
(ii) Pm3+
- Neutral Pm (Z = 61): [Xe]4f56s2
- Remove 3 electrons: from 6s (2 e⁻), then from 4f (1 e⁻)
- Pm3+: [Xe]4f4
(iii) Cu+
- Neutral Cu (Z = 29): [Ar]3d104s1 (Exception: fully filled d-subshell)
- Remove 1 electron: from 4s
- Cu+: [Ar]3d10
(iv) Ce4+
- Neutral Ce (Z = 58): [Xe]4f15d16s2 (Actual ground state: [Xe]4f15d16s2)
- Remove 4 electrons: from 6s (2 e⁻), then 5d (1 e⁻), then 4f (1 e⁻)
- Ce4+: [Xe] (noble gas core)
(v) Co2+
- Neutral Co (Z = 27): [Ar]3d74s2
- Remove 2 electrons: from 4s
- Co2+: [Ar]3d7
(vi) Lu2+
- Neutral Lu (Z = 71): [Xe]4f145d16s2
- Remove 2 electrons: from 6s (2 e⁻)
- Lu2+: [Xe]4f145d1
(vii) Mn2+
- Neutral Mn (Z = 25): [Ar]3d54s2
- Remove 2 electrons: from 4s
- Mn2+: [Ar]3d5
(viii) Th4+
- Neutral Th (Z = 90): [Rn]6d27s2
- Remove 4 electrons: from 7s (2 e⁻), then 6d (2 e⁻)
- Th4+: [Rn] (noble gas core)
Key Exam Insight
Stability of oxidation states is linked to half-filled (d5, f7) or fully filled (d10, f14) subshells.
For example:
- Mn2+ (d5) is stable → half-filled stability
- Cu+ (d10) is stable → fully filled stability
- Ce4+ ([Xe]) is stable → noble gas configuration
Here are the most common mistakes students make when writing electronic configurations for ions, especially in the context of Stability of Oxidation States (d- and f-block elements), and how to avoid each.
Mistake 1: Forgetting that electrons are removed from the 4s orbital first (for d-block ions)
The Error:
For Cr3+, writing [Ar]3d14s2 — removing all three electrons from 3d and leaving the 4s pair untouched.
The same wrong removal order turns Co2+ into [Ar]3d54s2 instead of the correct [Ar]3d7.
Why it happens:
Students memorise "4s is filled before 3d" but forget that when forming cations, electrons are removed from the 4s orbital first (because 4s is higher in energy once occupied).
How to avoid:
- For any d-block ion, always remove from 4s before 3d.
- Write the neutral atom configuration first, then strip the outermost s-electrons.
- Example:
- Neutral Cr: [Ar]3d54s1
- Cr3+: remove 1 from 4s, then 2 from 3d → [Ar]3d3
- Neutral Co: [Ar]3d74s2
- Co2+: remove 2 from 4s → [Ar]3d7
Mistake 2: Ignoring the stability of half-filled and fully-filled d-subshells
The Error:
For Cu+, students write [Ar]3d94s0 (which is technically possible) but miss that Cu+ is actually [Ar]3d10 (fully filled d — very stable).
Similarly, for Cr3+, they might write [Ar]3d24s1 instead of [Ar]3d3.
Why it happens:
They don't check if a half-filled (d5) or fully-filled (d10) configuration is possible after ionisation.
How to avoid:
- After removing electrons, check if the d-subshell becomes d5 or d10 — these are extra stable.
- For Cu+:
- Neutral Cu: [Ar]3d104s1
- Remove 1 electron (from 4s) → [Ar]3d10 (fully filled) — this is the correct configuration.
- For Cr3+:
- Neutral Cr: [Ar]3d54s1
- Remove 3 electrons (1 from 4s, 2 from 3d) → [Ar]3d3 (not half-filled, but correct).
Mistake 3: Writing f-block configurations with the wrong removal order (6s must go first)
The Error:
For Pm3+, students remove all three electrons from 4f, writing [Xe]4f26s2 instead of the correct [Xe]4f4 (remove the 6s pair first, then one 4f).
For Ce4+, they write [Xe]4f15d1 or [Xe]4f2 instead of [Xe] (empty f — f0).
For Lu2+, they remove the 5d electron first, writing [Xe]4f146s1 instead of the correct [Xe]4f145d1 (the 6s pair goes first).
Why it happens:
f-block elements have complex filling order (4f, 5d, 6s). Students forget that for lanthanides, the 4f is filled before 5d and 6s, and that stable oxidation states often correspond to f⁰, f⁷, f¹⁴.
How to avoid:
- For lanthanides (Ce to Lu), the neutral configuration is [Xe]4fn5d0 or [Xe]4fn−15d1 (exceptions: La, Gd, Lu).
- When forming ions, remove 6s electrons first, then 4f (if needed).
- Examples:
- Ce4+: Neutral Ce = [Xe]4f15d16s2 (or [Xe]4f26s2). Remove 4 electrons → [Xe] (f⁰ — very stable).
- Pm3+: Neutral Pm = [Xe]4f56s2. Remove 3 electrons (2 from 6s, 1 from 4f) → [Xe]4f4.
- Lu2+: Neutral Lu = [Xe]4f145d16s2. Remove 2 electrons (from 6s) → [Xe]4f145d1 (but note: Lu2+ is unstable; the stable ion is Lu3+ = [Xe]4f14).
Mistake 4: Confusing actinide configurations with lanthanides
The Error:
For Th4+, students write [Rn]5f06d07s0 (which is correct) but they might write [Rn]5f2 or [Rn]6d2 because they misremember the neutral configuration.
Why it happens:
Actinides have 5f, 6d, 7s filling that is less regular than lanthanides. Thorium (Th) is an exception: neutral Th = [Rn]6d27s2, not [Rn]5f2.
How to avoid:
- Memorise key exceptions:
- Th (Z=90): [Rn]6d27s2
- Pa (Z=91): [Rn]5f26d17s2
- U (Z=92): [Rn]5f36d17s2
- For Th4+: remove 4 electrons (2 from 7s, 2 from 6d) → [Rn] (noble gas core, f⁰ — very stable).
Mistake 5: Not checking for exceptions in neutral configurations before ionising
The Error:
For Cr3+, students start from [Ar]3d44s2 (wrong neutral Cr) and then remove 3 electrons → [Ar]3d34s0 (correct final, but wrong reasoning).
For Cu+, they start from [Ar]3d94s2 (wrong neutral Cu) → [Ar]3d9 (wrong).
Why it happens:
They don't memorise the anomalous configurations of Cr and Cu in the neutral state.
How to avoid:
- Memorise these neutral exceptions:
- Cr: [Ar]3d54s1 (not 3d44s2)
- Cu: [Ar]3d104s1 (not 3d94s2)
- Also: Nb, Mo, Ru, Rh, Pd, Ag, Pt, Au have similar anomalies.
- Always write the correct neutral configuration first, then remove electrons.
Quick Reference Table for the Given Ions
| Ion | Correct Configuration | Common Mistake |
|---|---|---|
| Cr3+ | [Ar]3d3 | [Ar]3d14s2 or [Ar]3d24s1 |
| Pm3+ | [Xe]4f4 | [Xe]4f5 or [Xe]4f35d1 |
| Cu+ | [Ar]3d10 | [Ar]3d94s0 |
| Ce4+ | [Xe] (f⁰) | [Xe]4f2 or [Xe]4f15d1 |
| Co2+ | [Ar]3d7 | [Ar]3d54s2 (wrong removal order) |
| Lu2+ | [Xe]4f145d1 (unstable) | [Xe]4f135d2 or [Xe]4f146s2 |
| Mn2+ | [Ar]3d5 | [Ar]3d34s2 |
| Th4+ | [Rn] (f⁰) | [Rn]5f2 or [Rn]6d2 |
Final Exam Tip
Always write the neutral configuration first, then remove electrons from the outermost s-orbital (and then d or f if needed). Check for half-filled/full-filled stability. For f-block, remember f⁰, f⁷, f¹⁴ are especially stable.
- AHSEC Higher Secondary (HS) Final Examination 2025Set ANNUAL2 marksQ.Which one is more reducing Cr2+ or Fe2+ and why?
›Reveal solutionSolution
Cr2+ readily loses an electron to become the more stable d3 Cr3+ (negative E°, strong reducing agent), whereas Fe2+ oxidising to Fe3+ is thermodynamically unfavourable (positive E°), so Fe2+ is only a weak reducing agent.
A more negative (or less positive) standard reduction potential for the M3+/M2+ couple means the M2+ ion more readily gives up an electron, i.e. it is a stronger reducing agent.
- E∘(Cr3+/Cr2+)=−0.41 V (negative) — this means Cr2+ is easily oxidised to Cr3+. This is because Cr3+ has the extra-stable half-filled t2g3 (d3) configuration, so the Cr2+ → Cr3+ oxidation is thermodynamically very favourable.
- E∘(Fe3+/Fe2+)=+0.77 V (positive) — this means Fe3+ is comparatively stable and does NOT readily accept an electron; conversely, Fe2+ is only a weak reducing agent, oxidising to Fe3+ with difficulty (Fe3+ does have a stable half-filled d5 configuration too, but not enough to make the potential negative).
Since Cr2+ has a much more negative reduction potential for its oxidised/reduced couple, it loses its electron far more readily than Fe2+ does.
✓Final answerCr2+ is the stronger (more) reducing agent, because oxidation of Cr2+ to the very stable d3 Cr3+ is thermodynamically much more favourable (E° = -0.41 V) than oxidation of Fe2+ to Fe3+ (E° = +0.77 V).
- AHSEC Higher Secondary (HS) Final Examination 2023Set ANNUAL2 marksQ.Why is Cr2+ reducing and Mn3+ oxidizing when both have d4 configuration? OR Out of Cu+ and Cu2+, which ion is more stable in aqueous solution and why?
›Reveal solutionSolution
Both options are explained by which resulting ion (after losing/gaining an electron, or by hydration) is thermodynamically more stable.
Option 1 — Cr²⁺ reducing, Mn³⁺ oxidising (both d⁴):
Cr2+ (3d⁴) tends to lose one electron and get oxidised to Cr3+ (3d³), because the d3 configuration (t2g3, all three lower-energy orbitals singly occupied) is a particularly stable, symmetric half-filled-t2g arrangement in an octahedral field. This driving force to reach a more stable d3 state makes Cr2+ a strong reducing agent.
Mn3+ (3d⁴) tends to gain one electron and get reduced to Mn2+ (3d⁵), because the exactly half-filled d5 configuration has extra stability (maximum exchange energy, all five d orbitals singly occupied). This strong tendency to gain an electron makes Mn3+ a strong oxidising agent.
So although both starting ions have the same d4 configuration, they move in opposite directions (Cr²⁺ loses an electron, Mn³⁺ gains one) because each is driven toward a more stable configuration — d3(t2g3) for chromium and d5 (half-filled) for manganese.
Option 2 — Cu⁺ vs Cu²⁺ stability in water:
Isolated Cu+ (3d¹⁰, fully-filled d subshell) looks like it should be the more stable ion electronically. However, in aqueous solution, stability is governed by overall thermodynamics, not just electronic configuration. Cu2+, being smaller and more highly charged, has a much larger (more negative) hydration enthalpy than Cu+. This extra hydration energy released more than compensates for the additional (second) ionisation energy required to remove an electron from Cu+ to form Cu2+.
As a result, Cu2+(aq) is thermodynamically more stable than Cu+(aq), and Cu+ actually disproportionates in aqueous solution: 2Cu+(aq)→Cu2+(aq)+Cu(s) — direct evidence that Cu2+ is the more stable aqueous species.
✓Final answerOption 1: Cr²⁺ is reducing (→ stable d³ Cr³⁺); Mn³⁺ is oxidising (→ stable half-filled d⁵ Mn²⁺). Option 2: Cu²⁺ is more stable than Cu⁺ in water, because its far greater hydration enthalpy outweighs the extra ionisation energy needed.
- AHSEC Higher Secondary (HS) Final Examination 2022Set ANNUAL2 marksQ.Answer the following questions (any two): When HCl reacts with finely powdered iron, it forms ferrous chloride, and not ferric chloride. Explain, why?
›Reveal solutionSolution
HCl dissolves iron by a simple acid-metal displacement reaction (Fe loses 2 electrons to H+), which can only reach the Fe2+ state; reaching Fe3+ would require a stronger oxidizing acid than HCl.
When finely powdered iron reacts with dilute hydrochloric acid, the reaction is a straightforward metal-acid displacement (redox) reaction:
Fe(s) + 2HCl(aq) → FeCl2(aq) + H2(g)↑
Here, Fe is oxidised by H⁺ ions: Fe → Fe²⁺ + 2e⁻, while 2H⁺ + 2e⁻ → H2. HCl (specifically, the H⁺ ion) is only a MODEST/weak oxidizing agent — it is capable of oxidising Fe only up to the Fe²⁺ (ferrous) state, which is the more easily accessible oxidation state for iron in this kind of simple acid dissolution.
To oxidise iron further, all the way to Fe³⁺ (ferric), a STRONGER oxidizing agent is required — such as concentrated (oxidizing) HNO3, or chlorine gas (Cl2) reacting directly with iron, both of which have the oxidizing power to remove the additional electron needed to reach Fe³⁺. Ordinary dilute HCl simply lacks this oxidizing strength, so the product remains FeCl2, not FeCl3.
✓Final answerFe + 2HCl → FeCl2 + H2 — dilute HCl is only a weak (non-oxidizing beyond H⁺/H2) acid, capable of oxidising Fe only to Fe2+ (FeCl2); reaching Fe3+ (FeCl3) needs a stronger oxidizing agent, such as conc. HNO3 or Cl2 gas.
- AHSEC Higher Secondary (HS) Final Examination 2020Set ANNUAL2 marksQ.Why is Cr2+ reducing and Mn3+ oxidizing when both have d4 configuration?
›Reveal solutionSolution
Although both Cr2+ and Mn3+ have a d4 configuration, they behave oppositely because each is being "pulled" towards a different, more stable neighbouring configuration: Cr2+ loses an electron to reach the stable t2g³ arrangement of Cr3+, while Mn3+ gains an electron to reach the extra-stable half-filled d5 configuration of Mn2+.
Cr2+ is a reducing agent
Cr2+ has the electronic configuration [Ar]3d4. When it loses one electron, it becomes Cr3+, which has the configuration [Ar]3d3, corresponding (in an octahedral field) to the arrangement t2g³eg⁰. A t2g³ configuration, with three electrons singly occupying the three lower-energy t2g orbitals, is particularly stable. Because Cr3+ (d3) is markedly more stable than Cr2+ (d4), Cr2+ readily loses an electron to become Cr3+ — that is, Cr2+ is easily oxidised, making it a good reducing agent.
Mn3+ is an oxidising agent
Mn3+ also has the configuration [Ar]3d4. When it gains one electron, it becomes Mn2+, with configuration [Ar]3d5 — a half-filled d-subshell, in which all five d orbitals are singly occupied. A half-filled d-subshell is exceptionally stable due to maximum exchange energy and symmetric charge distribution. Because Mn2+ (d5) is much more stable than Mn3+ (d4), Mn3+ readily accepts an electron to become Mn2+ — that is, Mn3+ is easily reduced, making it a good oxidising agent.
Summary
Both ions start at d4, an inherently less stable configuration, but each moves towards stability in the opposite direction: Cr2+ moves "down" by oxidation (losing an electron) to reach the stable d3 (t2g³) state, while Mn3+ moves "up" by reduction (gaining an electron) to reach the stable, half-filled d5 state.
✓Final answerCr2+ (d4 → d3 on oxidation) is reducing because Cr3+'s t2g³ configuration is extra stable. Mn3+ (d4 → d5 on reduction) is oxidising because Mn2+'s half-filled d5 configuration is extra stable.
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