Q.The electronic configuration of Cu(II) is 3d9 whereas that of Cu(I) is 3d10. Which of the following is correct?
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.
The key idea is that stability depends on more than just a filled d-subshell — it also involves hydration energy and lattice energy effects.
Step 1: Cu(I) has a 3d10 configuration, which is fully filled and appears stable. Cu(II) has 3d9, an incomplete subshell.
Step 2: In aqueous solution, Cu(II) is more stable because its higher charge (+2) gives a much larger hydration energy, which compensates for the loss of a filled d-shell.
Step 3: In the solid state, Cu(II) compounds often have higher lattice energies. Overall, Cu(II) is the more common and stable oxidation state in most conditions.
Cu(II) is more stable than Cu(I) in aqueous medium.
The key idea is that while a fully filled 3d10 subshell (Cu(I)) is stable, the higher charge and smaller size of Cu(II) give it a much larger hydration enthalpy in aqueous solution, which more than compensates for the energy cost of removing an extra electron. In aqueous medium, Cu(II) is more stable than Cu(I).
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Start with the electronic configurations.
Cu(I) has the configuration 3d10 — a completely filled d-subshell. Cu(II) has 3d9 — one electron short of a full d-subshell. A filled subshell is inherently more stable due to exchange energy and symmetry. So, in the gas phase, Cu(I) is more stable than Cu(II). If the question were about gaseous ions, Cu(I) would win.
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But the real world is not the gas phase — it's aqueous solution.
Most common chemistry of copper happens in water. Here, the stability of an ion depends not just on its electronic configuration, but also on its hydration enthalpy — the energy released when water molecules surround the ion. The hydration enthalpy depends on two factors: charge and ionic radius. Higher charge and smaller size both increase hydration enthalpy.
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Compare Cu(I) and Cu(II) in terms of charge and size.
Cu(II) has a +2 charge, while Cu(I) has only +1. Also, Cu(II) has a smaller ionic radius (about 73 pm) compared to Cu(I) (about 96 pm). The combination of higher charge and smaller size means Cu(II) has a much larger hydration enthalpy than Cu(I).
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The energy balance.
To go from Cu(I) to Cu(II), you need to remove one more electron — that costs ionization energy. But the huge hydration enthalpy of Cu(II) more than makes up for this cost. The net result is that in water, Cu(II) is thermodynamically more stable than Cu(I).
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Evidence from disproportionation.
Cu(I) in aqueous solution spontaneously disproportionates:
2Cu+(aq)→Cu(s)+Cu2+(aq)
This reaction is thermodynamically favorable (positive E∘), which directly shows that Cu(II) is more stable than Cu(I) in water.
A common mistake is to stop at the electronic configuration and conclude that Cu(I) with 3d10 must be more stable. That is true only for gaseous ions. In solution, the hydration effect reverses the stability order.
For transition metals, always check the medium. In aqueous solution, higher oxidation states are often stabilized by hydration or complexation, even if the gas-phase configuration suggests otherwise.
The correct option is (i) Cu(II) is more stable.
Method: Stability Analysis Using Electronic Configuration & Hydration Energy
Step 1: Compare electronic configurations
- Cu(I) → 3d10 → fully filled d-subshell (stable configuration)
- Cu(II) → 3d9 → one electron less than fully filled
At first glance, Cu(I) appears more stable due to the completely filled d-orbital.
Step 2: Consider the real-world stability in aqueous medium
In aqueous solution, Cu(II) is more stable than Cu(I). Why?
- Cu(II) has higher charge (+2) and smaller ionic radius than Cu(I).
- This leads to much higher hydration enthalpy for Cu(II), which compensates for the loss of the stable 3d10 configuration.
Step 3: Check disproportionation tendency
Cu(I) in aqueous solution undergoes disproportionation:
2Cu+→Cu+Cu2+
This reaction is spontaneous, confirming that Cu(II) is more stable in solution.
Step 4: Conclusion
Despite the fully filled 3d10 configuration of Cu(I), the higher hydration energy of Cu(II) makes it the more stable oxidation state in aqueous medium.
Correct option: (i) Cu(II) is more stable
Here are the common mistakes students make on this question, along with how to avoid each.
Mistake 1: Assuming Full d-subshell Always Means Higher Stability
- The Mistake: Students see that Cu(I) has a 3d10 configuration (completely filled d-subshell) and immediately assume it must be more stable than Cu(II) with 3d9. They pick option (ii) "Cu(II) is less stable" without further thought.
- Why it's Wrong: While a fully filled d-subshell does provide extra stability, it is not the only factor. In transition metals, the hydration enthalpy (energy released when ions dissolve in water) and lattice energy (for solid compounds) often outweigh the stability gained from a filled d-subshell.
- How to Avoid: Remember the "exceptions" in transition metal chemistry. For copper, Cu(II) is actually more stable in aqueous solution and in most of its salts. Always check the real-world behavior of the element, not just the theoretical electron configuration.
Mistake 2: Ignoring the Role of Hydration Enthalpy
- The Mistake: Students forget to consider what happens when the ion is in solution. They treat the stability as an isolated property of the ion in a vacuum.
- Why it's Wrong: The question is about stability in a general chemical context. Cu(II) has a higher charge (+2) and a smaller ionic radius than Cu(I). This means it has a much higher hydration enthalpy (the energy released when water molecules surround the ion). This large energy release compensates for the loss of the filled d-subshell, making Cu(II) more stable in water.
- How to Avoid: When comparing stability of different oxidation states of transition metals, always ask: "What is the environment?" For aqueous solutions, higher charge density often leads to greater stability due to hydration energy. Write down the formula: Stability = (Electronic Configuration Stability) + (Hydration/Lattice Energy).
Mistake 3: Confusing "Stability" with "Ease of Formation"
- The Mistake: Students think that because Cu(I) is formed first (e.g., from Cu metal), it must be more stable.
- Why it's Wrong: Cu(I) is often an intermediate that quickly disproportionates (self-oxidizes and reduces) into Cu(II) and Cu metal. The fact that Cu(I) is hard to isolate in water shows it is less stable under those conditions.
- How to Avoid: Understand that stability refers to the tendency of a species to remain as it is, not how easily it is formed. A species can be formed easily but be highly unstable (like Cu(I) in water). Focus on the final, predominant species.
Mistake 4: Misinterpreting the "d^10" Exception
- The Mistake: Students overgeneralize the stability of d10 configurations. They apply it blindly to all elements (e.g., Zn, Cd, Hg) and assume it works the same for copper.
- Why it's Wrong: For Zn, d10 is indeed the most stable state (+2). But for Cu, the +2 state is more stable despite having d9. The difference is that Cu has a smaller nuclear charge and different ionic radii, making the +2 state energetically favorable in water.
- How to Avoid: Treat each element as a unique case. Memorize the key exceptions: Cu(II) > Cu(I) in water, Fe(III) > Fe(II) in some complexes, etc. Don't rely on a single rule for all transition metals.
The Correct Answer and Why
The correct answer is (i) Cu(II) is more stable.
- Reason: In aqueous solution and in most of its compounds, Cu(II) is more stable than Cu(I) due to the much higher hydration enthalpy of Cu(II) (which has a higher charge and smaller size). This energy gain outweighs the stability provided by the 3d10 configuration of Cu(I). Cu(I) compounds often disproportionate in water to give Cu(II) and Cu metal.
Key Takeaway: For copper, Cu(II) is the more stable oxidation state in water, despite having an incomplete d-subshell. Always consider the environment (aqueous vs. solid) and the energy contributions from hydration or lattice formation.
- 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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