Q.In the form of dichromate, Cr(VI) is a strong oxidising agent in acidic medium but Mo(VI) in MoO3 and W(VI) in WO3 are not because ___________.
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🔒 Start your 14-day free trial to unlock the full solution →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 …
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: …
Concept: Stability of Oxidation States — In transition series, higher oxidation states become more stable down a group due to increased shielding and less tendency to get reduced.
Reasoning:
- Cr(VI) in acidic medium is a strong oxidising agent because it readily gets reduced to Cr(III) — the +6 state is less stable for Cr.
- For Mo and W, the +6 state is much more stable due to better overlap of 4d/5d orbitals and weaker oxidising power. …
The key idea is the stability of higher oxidation states increases down a group in transition series. Cr(VI) is a strong oxidising agent because it is less stable and readily reduces, while Mo(VI) and W(VI) are more stable and thus not strongly oxidising. The correct option is (iii).
The question asks why Cr(VI) in dichromate is a powerful oxidising agent in acidic medium, but Mo(VI) in MoO3 and W(VI) in WO3 are not. This is a classic example of a trend in the transition series — the stability of higher oxidation states.
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Understand the trend in stability of oxidation states.
In the d-block, as you move down a group (from 3d → 4d → 5d series), the higher oxidation states become more stable. This happens because the heavier transition metals have larger atomic radii and their d-orbitals are more diffuse, which allows them to share electrons more effectively with oxygen and form strong bonds. For example, Cr(VI) is less stable than Mo(VI) and W(VI).
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Relate stability to oxidising power.
A species that is less stable in a high oxidation state tends to gain electrons easily (i.e., it is a strong oxidising agent). Conversely, a species that is more stable in a high oxidation state resists reduction and is a weak oxidising agent.
- Cr(VI) (as Cr2O72−) is relatively unstable in acidic medium and readily reduces to Cr(III), making it a strong oxidiser.
- Mo(VI) and W(VI) are much more stable in their +6 states, so they do not readily accept electrons — hence they are not strong oxidising agents.
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Evaluate the given options.
- (i) Cr(VI) is more stable than Mo(VI) and W(VI) — this is false; it's the opposite.
- (ii) Mo(VI) and W(VI) are more stable than Cr(VI) — this is true in terms of stability, but the question asks why Cr(VI) is a strong oxidiser while the others are not. The reason is the trend in stability, not just the fact itself. …
Method: Stability Trend in Transition Metal Oxidation States
This question is solved using the concept of relative stability of higher oxidation states down a group in the d-block.
Steps:
-
Recall the general trend
In transition series, the stability of higher oxidation states (like +6) increases down the group.
- This is because the heavier elements (Mo, W) have larger atomic radii and more diffuse d-orbitals, which can better accommodate the loss of electrons without destabilising the atom.
-
Apply to Group-6 (Cr, Mo, W)
- Cr(VI) is less stable than Mo(VI) and W(VI).
- Hence, Cr(VI) is a strong oxidising agent — it readily gets reduced to Cr(III). …
Here’s a breakdown of the common mistakes students make on this question, along with how to avoid each.
Mistake 1: Confusing “Stability” with “Oxidising Power”
- The Error: Students see that Cr(VI) is a strong oxidising agent and assume this means Cr(VI) is more stable than Mo(VI) or W(VI). They then pick option (i).
- Why it’s wrong: An oxidising agent is strong because it is unstable and wants to get reduced. If Cr(VI) were more stable, it would not readily accept electrons.
- How to Avoid: Remember the inverse relationship:
- High stability → Weak oxidising agent (hard to reduce).
- Low stability → Strong oxidising agent (easy to reduce).
- Since Cr(VI) is a strong oxidiser, it is less stable than Mo(VI) and W(VI).
Mistake 2: Forgetting the Trend Down the Group
- The Error: Students memorise that “higher oxidation states are stable for heavier elements” but then apply it incorrectly. They might pick option (iii) but fail to connect it to the oxidising power logic.
- Why it’s wrong: The correct trend is that stability of the +6 oxidation state increases down Group 6 (Cr < Mo < W). This means Mo(VI) and W(VI) are more stable, not less.
- How to Avoid: Draw a mental arrow:
- Down Group 6: Stability of +6 state increases.
- Therefore: Oxidising power of +6 state decreases.
- So: Cr(VI) is the strongest oxidiser; W(VI) is the weakest.
Mistake 3: Misinterpreting the “Why” Behind the Trend
- The Error: Students think the trend is random or just based on atomic size. They don’t connect it to the inert pair effect or shielding.
- Why it’s wrong: The actual reason involves the poor shielding by d- and f-electrons in heavier elements. For Mo and W, the 4d and 5d orbitals are more diffuse, making the +6 state more stable relative to Cr’s compact 3d orbitals.
- How to Avoid: Link the concept to periodicity:
- For 3d series (Cr): Smaller size, poor shielding → +6 state is highly oxidising.
- For 4d/5d series (Mo, W): Larger size, better shielding → +6 state is more stable and less oxidising.
Mistake 4: Picking the Wrong Option Due to Wording …
- AP EAPCET 2026Set eng-2026-05-18-FN1 markMCQQ.Identify the pair of ions which act as good reducing agents (A) Ce4+,Yb2+ (B) Ce4+,Tb4+ (C) Ce3+,Tb2+ (D) Eu2+,Yb2+
›Reveal solutionSolution
This tests which unusual lanthanide oxidation states behave as reducing vs oxidising agents; Eu2+ and Yb2+ are the textbook pair of reducing agents, so the answer is (D).
Concept and Intuition
Lanthanides normally exist as Ln3+. A few elements also show +2 or +4 states when that unusual state happens to correspond to an especially stable f0, f7 (half-filled) or f14 (fully-filled) configuration. But "isolable" is not the same as "thermodynamically preferred" — the normal +3 state is still the most stable overall for the element, so:
- An unusual +4 ion (higher than normal +3) tends to gain an electron and fall back to +3 — it therefore acts as an oxidising agent (itself gets reduced). Examples: Ce4+ (4f0→4f1), Tb4+ (4f7→4f8).
- An unusual +2 ion (lower than normal +3) tends to lose an electron and rise back to +3 — it therefore acts as a reducing agent (itself gets oxidised). Examples: Eu2+ (4f7→4f6), Yb2+ (4f14→4f13), and (more weakly) Sm2+.
Step-by-Step Solution
- Identify each ion's usual/unusual character: Ce4+ (unusual +4, oxidiser), Tb4+ (unusual +4, oxidiser), Eu2+ (unusual +2, reducer), Yb2+ (unusual +2, reducer).
- Option (A) Ce4+,Yb2+ — mixes an oxidiser with a reducer, not a matching pair.
- Option (B) Ce4+,Tb4+ — both are oxidising agents, not reducing. …
- AP EAPCET 2026Set ap-2026-05-20-AN1 markMCQQ.Which pair of ions act as strong reducing agents? (A) Ce4+,Tb4+ (B) Eu2+,Yb2+ (C) Gd3+,Lu3+ (D) La3+,Pm3+
›Reveal solutionSolution
Eu2+ and Yb2+ are strong reducing agents because oxidising to the common +3 lanthanide state gives them extra electronic stability.
Concept and Intuition
Lanthanides are overwhelmingly found in the +3 oxidation state. Ions that deviate from +3 tend to revert to it if doing so gives a specially stable electron configuration (empty, half-filled, or fully-filled f subshell). Eu2+ (4f7, half-filled — already quite stable) still readily loses an electron to Eu3+ (4f6) — actually, more precisely, the drive is that +2 ions with configurations one electron short of a stable count are pushed to lose an electron toward +3, or +4 ions are pulled to gain one toward +3. The exam-relevant memorised fact: Eu2+ and Sm2+ (and here, Yb2+, which is 4f14, fully filled) act as reducing agents by oxidising to +3, while Ce4+ and Tb4+ act as oxidising agents by being reduced to the stable +3 state (Ce3+ is 4f0; Tb3+ is 4f8/near half-filled +1 pattern that's more stable than Tb4+).
Step-by-Step Solution
- Recall the standard exceptions to +3 among lanthanides: Ce4+,Pr4+,Tb4+ (oxidising agents, reduce to +3) and Eu2+,Sm2+,Yb2+ (reducing agents, oxidise to +3).
- Option (A) Ce4+,Tb4+ — both oxidising agents, not reducing. …
- AP EAPCET 2025Set eng-2025-05-22-FN1 markMCQQ.How many of the following lanthanide elements exhibit +4 oxidation state ? Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy (A) 5 (B) 4 (C) 3 (D) 6
›Reveal solutionSolution
Tests which lanthanides depart from the dominant +3 state to also show +4, based on electronic-configuration stability.
Concept and Intuition
Lanthanides are overwhelmingly +3 because that oxidation state matches a filled 6s/5d loss while leaving a reasonably stable 4f configuration. A few members show +4 (or +2) only when losing (or gaining) one more electron gets them to, or close to, an empty (f0), half-filled (f7), or fully-filled (f14) 4f sub-shell — extra stability that offsets the higher ionisation energy.
Step-by-Step Solution
- Ce (4f¹5d¹6s²): losing one more electron beyond +3 gives Ce⁴⁺ with f0 — very stable, +4 is in fact its best-known state (e.g., CeO2).
- Pr and Nd: Pr⁴⁺ (f1) and Nd⁴⁺ (f2) are known, though less stable than Ce⁴⁺ (e.g., PrO2, and Nd⁴⁺ in a few solid oxides).
- Pm: radioactive, poorly characterised; +4 not established.
- Sm, Eu: these instead favour +2 (f6 close to half-filled for Sm²⁺, and f7 half-filled exactly for Eu²⁺) — the opposite direction, not +4. …
- AP EAPCET 2023Set eng-2023-05-19-FN1 markMCQQ.Identify the correct statement (A) Yb2+ is an oxidant (B) Lu3+ is paramagnetic (C) CrO is basic (D) Brass is an alloy of Cu, Sn
›Reveal solutionSolution
Of the four statements, only "CrO is basic" is correct — the others misstate Yb2+'s redox role, Lu3+'s magnetism, and brass's composition.
Concept and Intuition
This question tests several standard d- and f-block facts together: (i) lanthanide ions in unusual oxidation states tend to revert to the characteristic, most stable +3 state, so Eu2+/Yb2+ act as reducing agents (they get oxidized to +3) while Ce4+/Tb4+ act as oxidizing agents (they get reduced to +3);
(ii) magnetism of lanthanide ions follows from unpaired 4f electrons — a fully-filled or fully-empty 4f subshell is diamagnetic;
(iii) the acid-base character of transition-metal oxides follows their oxidation state — low oxidation states give basic oxides, high oxidation states give acidic oxides, with intermediate ones amphoteric;
(iv) common alloy compositions (brass vs bronze) are a factual recall point.
Step-by-Step Solution
- (A) Yb2+: has configuration 4f14 (fully filled, stable), so it readily loses an electron to attain the general lanthanide-favoured Yb3+ state — meaning Yb2+ itself gets oxidized, i.e. it is a reducing agent, not an oxidant. Statement false.
- (B) Lu3+: Lu (Z=71) is [Xe]4f145d16s2; removing 3 electrons (5d1,6s2) gives Lu3+=[Xe]4f14 — completely filled 4f, hence diamagnetic, not paramagnetic. Statement false. …
- AP EAPCET 2022Set eng-2022-07-08-AN1 markMCQQ.For which of the following +3 oxidation state is highly oxidizing in character? (A) Al (B) Ga (C) In (D) Tl
›Reveal solutionSolution
The inert pair effect is strongest for the heaviest Group 13 element, thallium, making its +3 oxidation state a strong oxidizer that is readily reduced to the more stable +1 state.
Concept and Intuition
Going down Group 13 (B, Al, Ga, In, Tl), the ns² electron pair becomes increasingly reluctant to participate in bonding due to poor shielding by intervening d/f electrons and relativistic contraction of the ns orbital — this is the "inert pair effect". Consequently, the +1 oxidation state (where the ns² pair stays un-ionized) becomes progressively more stable relative to +3 as we move down the group. For Al and Ga, the +3 state is the dominant, stable state. For Tl, the inert pair effect is so pronounced that +1 is actually the more stable oxidation state, which means Tl(III) compounds are strong oxidizing agents — they are readily reduced to Tl(I), releasing energy in the process.
Step-by-Step Solution
- Rank the inert pair effect across Al, Ga, In, Tl — it strengthens down the group, being negligible for Al and dominant for Tl.
- For Al, +3 is essentially the only common, stable oxidation state (Al³⁺ is not oxidizing).
- For Ga and In, +3 is still the more stable state, with +1 being a minor, less common state. …
- AP EAPCET 2021Set ap-2021-10-05-FN1 markMCQQ.Which among the following is the strongest oxidizing agent? (A) SnO2 (B) SiO2 (C) GeO2 (D) PbO2
›Reveal solutionSolution
The inert-pair effect destabilises Pb(IV) relative to Pb(II), making PbO2 a strong oxidising agent — the strongest among SnO2, SiO2, GeO2, PbO2.
Concept and Intuition
Down group 14, the ns² electron pair becomes increasingly reluctant to participate in bonding (the inert-pair effect), so the lower oxidation state (+2) becomes progressively more stable relative to the group oxidation state (+4) as you go from C to Pb. This means Pb4+ compounds readily oxidise other species while being reduced to the more stable Pb2+.
Step-by-Step Solution
- SiO2, GeO2: silicon and germanium show little inert-pair effect; +4 is their stable, common state, so these oxides are not strong oxidisers.
- SnO2: tin shows a mild inert-pair effect; Sn4+ is reasonably stable, only a weak oxidiser. …
- AP EAPCET 2021Set eng-2021-08-19-AN1 markMCQQ.The incorrect statement among the following is /are ________ (A) NCl5 does not exist while PCl5 does (B) Pb prefers to form tetravalent compounds (C) The three C−O bonds are equal in the CO32− ion (D) Both O2+ and NO are paramagnetic
›Reveal solutionSolution
The inert-pair effect makes lead prefer the +2 (divalent) oxidation state, not +4 (tetravalent) — so the claim that "Pb prefers to form tetravalent compounds" is the incorrect statement.
Concept and Intuition
Going down Group 14, the heavier elements' ns2 electron pair becomes increasingly reluctant to participate in bonding (the inert-pair effect, due to poor shielding by intervening d/f electrons and relativistic contraction of the ns orbital). This makes the lower oxidation state progressively more stable for heavier members: Sn shows both +2 and +4 fairly readily, but Pb strongly favours +2 (PbO, PbCl2, Pb(NO3)2 are common; Pb4+ compounds like PbO2 are comparatively strong oxidizers/less stable).
Step-by-Step Solution
- (A) NCl5 does not exist (N has no accessible d orbitals to expand its octet beyond 4 bonds) while PCl5 does (P can use 3d orbitals) — this is a correct/true statement.
- (B) "Pb prefers to form tetravalent compounds" — false; due to the inert-pair effect Pb actually prefers divalent compounds. This is the incorrect statement. …
- AP EAPCET 2021Set eng-2021-08-24-FN1 markMCQQ.The stability of +1 oxidation state increases in the sequence ________ (A) Ga<In<Al<Tl (B) Al<Ga<In<Tl (C) Tl<In<Ga<Al (D) In<Tl<Ga<Al
›Reveal solutionSolution
The inert-pair effect grows down group 13, making the +1 oxidation state progressively more stable: least for Al, most for Tl.
Concept and Intuition
The inert-pair effect describes the reluctance of the outermost ns2 electron pair to participate in bonding as atomic number increases down a group, due to poor shielding by intervening d/f electrons and relativistic effects for heavier elements. In group 13, this makes the +1 oxidation state (retaining the ns2 pair, only losing the single p electron) increasingly favoured relative to +3 as you go down the group.
Step-by-Step Solution
- Al: +3 is overwhelmingly the stable/common oxidation state; +1 compounds are rare and unstable.
- Ga: +1 exists but is less stable than +3; +3 still dominant.
- In: +1 and +3 are both reasonably common, with +1 gaining stability. …
- AP EAPCET 2021Set eng-2021-08-25-FN1 markMCQQ.Among the following options, identify the one which exhibits the greatest number of oxidation states. (A) Fe (B) Mn (C) Cr (D) V
›Reveal solutionSolution
Manganese exhibits the broadest range of oxidation states among first-row transition metals. Answer: Mn.
Concept and Intuition
The number of oxidation states a transition metal can adopt tends to be maximised near the middle of the 3d series, where there are enough d-electrons to support both low and (through loss of many/all valence electrons) very high oxidation states, while still having partially-filled d-orbitals available for a range of intermediate states. Manganese, with configuration 3d54s2, is the textbook example, spanning +2 (as Mn2+) all the way to +7 (as MnO4−).
Step-by-Step Solution
- V (Z=23): common oxidation states +2,+3,+4,+5 — 4 common states.
- Cr (Z=24): common oxidation states +2,+3,+6 (and +4,+5 less commonly) — fewer well-established states than Mn. …
- AP EAPCET 2021Set eng-2021-10-05-FN1 markMCQQ.The most common oxidation state among lanthanoids is ______ (A) +4 (B) +3 (C) +2 (D) +1
›Reveal solutionSolution
Almost all lanthanoids show a dominant +3 oxidation state because losing the 6s2 (and 5d1 where present) electrons is comparatively easy, while removing a 4th electron from the deeply shielded 4f subshell requires a very high ionisation energy.
Concept and Intuition
The chemistry of lanthanoids is governed by the filling of the inner 4f subshell, which is well shielded from the surrounding chemical environment by the outer 5s25p6 shells. Because the 4f electrons are so shielded, they don't participate readily in bonding, and it is always the outermost 6s2 electrons (plus the occasional 5d1) that ionise first.
Step-by-Step Solution
- General configuration: [Xe]4f1−145d0,16s2.
- First two ionisations remove 6s2 readily; where a 5d1 electron is present it is the third to go — giving the Ln3+ ion with configuration [Xe]4fn.
- The 4th ionisation energy (removing an electron from 4fn) is very large, because the 4f subshell is already at a comparatively stable, contracted low-energy configuration once the outer electrons are gone. …
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