Q.Although Cr3+ and Co2+ ions have same number of unpaired electrons but the magnetic moment of Cr3+ is 3.87 B.M. and that of Co2+ is 4.87 B.M. Why?
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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: …
The key idea is that magnetic moment depends not only on the number of unpaired electrons but also on the orbital contribution, which varies with the electronic configuration and the ligand field.
Reasoning:
-
Number of unpaired electrons: Both Cr3+ (d3) and Co2+ (d7) have three unpaired electrons in their ground states.
- Cr3+: t2g3 (all unpaired).
- Co2+ (high-spin): t2g5eg2 — three unpaired electrons.
-
Spin-only formula: The spin-only magnetic moment is μ=n(n+2) B.M. For n=3, this gives 3×5=15≈3.87 B.M.
-
Orbital contribution:
- Cr3+ has a 4F ground term with L=3, but in an octahedral field the orbital angular momentum is largely quenched (the t2g3 configuration has no orbital degeneracy in a cubic field). Hence μ matches the spin-only value (3.87 B.M.). …
The magnetic moment depends on both the number of unpaired electrons and the orbital contribution. Cr3+ has no orbital contribution (quenched by crystal field), while Co2+ retains a significant orbital contribution, giving a higher magnetic moment despite the same number of unpaired electrons.
The key here is that magnetic moment is not simply a function of the number of unpaired electrons — it also depends on whether the orbital angular momentum contributes to the total moment. For transition metal ions in complexes, the crystal field can "quench" the orbital contribution, but not always.
Let’s break this down.
- The spin-only formula For an ion with n unpaired electrons, the spin-only magnetic moment is:
μs.o.=n(n+2)B.M.
For n=3, this gives 3×5=15≈3.87 B.M.
So Cr3+ matches the spin-only value exactly. That tells us immediately that its orbital angular momentum is completely quenched.
-
Why is Cr3+ spin-only?
Cr3+ has the electronic configuration [Ar]3d3. In an octahedral crystal field, the three electrons occupy the t2g orbitals (dxy,dyz,dzx) with parallel spins (Hund’s rule).
The t2g set is triply degenerate, but in a perfect octahedral field, the orbital angular momentum is quenched because the orbitals are real (not complex) and the ground term is 4A2g — an orbital singlet. No orbital degeneracy means no orbital contribution.
-
Now Co2+: same n, different story
Co2+ has the configuration [Ar]3d7. In an octahedral field, this is t2g5eg2. The ground term is 4T1g(F) — an orbital triplet.
The T1g term has orbital angular momentum that is not fully quenched. The magnetic moment is therefore higher than the spin-only value. The experimental value of 4.87 B.M. is close to what is expected when spin-orbit coupling mixes in some orbital contribution.
A quick way to check: if the ground term symbol has A (as in 4A2g), orbital contribution is zero. If it has T (as in 4T1g), orbital contribution is present and the magnetic moment will exceed the spin-only value.
- Quantifying the difference For Co2+ in an octahedral field, the effective magnetic moment is given by:
μeff=μs.o.(1−Δαλ)
where λ is the spin-orbit coupling constant (negative for d7), Δ is the crystal field splitting, and α is a factor depending on the term. The negative λ and the mixing cause μeff to be larger than μs.o.. …
Method: Spin-Only Magnetic Moment Calculation
This problem is solved using the spin-only formula for magnetic moment, combined with the electronic configuration of each ion.
Step 1 – Recall the spin-only formula
The magnetic moment μ (in Bohr Magnetons, B.M.) for a transition metal ion is given by:
μ=n(n+2)
where n = number of unpaired electrons.
This formula assumes that orbital angular momentum is quenched (i.e., not contributing), which is often true for first-row transition metals in complexes.
Step 2 – Find the electronic configuration of each ion
-
Cr³⁺:
Atomic number of Cr = 24
Ground state: [Ar]3d54s1
After losing 3 electrons (2 from 4s and 1 from 3d):
[Ar]3d3
Number of unpaired electrons = 3
-
Co²⁺:
Atomic number of Co = 27
Ground state: [Ar]3d74s2
After losing 2 electrons (from 4s):
[Ar]3d7
In a weak field (high spin) environment, the 3d⁷ configuration gives:
Number of unpaired electrons = 3
Step 3 – Apply the formula for each
- For Cr³⁺ (n=3):
μ=3(3+2)=15≈3.87 B.M.
- For Co²⁺ (n=3):
μ=3(3+2)=15≈3.87 B.M.
Step 4 – Identify the reason for the discrepancy
The spin-only formula gives 3.87 B.M. for both, but the observed value for Co²⁺ is 4.87 B.M.
Why? …
✗ Mistake 1: Assuming same number of unpaired electrons means same magnetic moment
Why it's wrong:
Magnetic moment (μ) depends not just on the number of unpaired electrons (n), but also on the orbital contribution (via the spin–orbit coupling). The formula μ=n(n+2) assumes only spin contribution — this works for most first-row transition metals, but not always.
How to avoid:
Always check if the ion is in a weak field or strong field environment, and whether orbital angular momentum is quenched or not. For Co2+ in an octahedral field, there is an orbital contribution that increases μ beyond the spin-only value.
✗ Mistake 2: Forgetting the electronic configuration details
Why it's wrong:
Students often write Cr3+ as [Ar]3d3 and Co2+ as [Ar]3d7 — correct so far. But then they assume both have 3 unpaired electrons and stop there. They miss that the arrangement of electrons in t2g and eg orbitals affects orbital angular momentum.
How to avoid:
Draw the d-orbital splitting diagram for each ion in an octahedral field:
- Cr3+ (d3): All three electrons go into t2g (one each) — all unpaired, but no orbital degeneracy → no orbital contribution.
- Co2+ (d7): High-spin configuration: t2g5eg2 — this has orbital degeneracy in the t2g set → orbital angular momentum is not fully quenched.
✗ Mistake 3: Using the spin-only formula blindly
Why it's wrong:
For Cr3+: n=3, so μ=3(3+2)=15≈3.87 B.M. — matches.
For Co2+: n=3, same formula gives 3.87 B.M., but the actual value is 4.87 B.M. — the formula fails here.
How to avoid:
Remember: The spin-only formula works well when orbital angular momentum is quenched (common for d3, d5, d8 high-spin, d6 low-spin). For d7 high-spin (like Co2+), orbital contribution is significant — use the formula μ=4S(S+1)+L(L+1) or simply memorise the experimental trend.
✗ Mistake 4: Confusing high-spin vs low-spin
Why it's wrong: …
- 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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