Q.[Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2− is diamagnetic. Explain 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 crystal field splitting — the magnetic behaviour depends on the number of unpaired electrons left in the d-orbitals after ligand-field splitting.
- [Cr(NH3)6]3+: Cr is in the +3 oxidation state, giving a d3 configuration. NH3 is a moderate field ligand — and for a d3 system the field strength does not even matter: in an octahedral field the three electrons occupy the three t2g orbitals singly (Hund’s rule), so no pairing can occur either way. This leaves three unpaired electrons, making the complex paramagnetic. …
The magnetic behaviour depends on the crystal field splitting and the electronic configuration of the central metal ion. [Cr(NH3)6]3+ is paramagnetic because it has three unpaired electrons in a weak-field octahedral environment, while [Ni(CN)4]2− is diamagnetic because it has zero unpaired electrons in a strong-field square planar geometry.
Why This Approach Works
The key to predicting magnetic behaviour lies in understanding how ligands influence the d-orbital splitting of the central metal ion. Paramagnetism arises from unpaired electrons — the more unpaired electrons, the stronger the paramagnetic effect. Diamagnetism, on the other hand, occurs when all electrons are paired.
Two factors determine whether electrons remain unpaired or get forced into pairs:
- Crystal field splitting energy (Δ) — how much the d-orbitals split in energy
- Pairing energy (P) — the energy cost to put two electrons in the same orbital
When Δ<P (weak field), electrons follow Hund's rule and occupy orbitals singly first — giving maximum unpaired electrons. When Δ>P (strong field), electrons pair up in lower-energy orbitals before occupying higher ones — giving fewer or zero unpaired electrons.
Let's apply this to each complex.
Step-by-Step Reasoning
1. Determine the oxidation state and d-electron count for each complex
For [Cr(NH3)6]3+:
- NH3 is neutral, so the charge comes entirely from Cr.
- Cr is in +3 oxidation state.
- Cr atomic number = 24. Electronic configuration: [Ar]3d54s1.
- Cr3+ loses three electrons: the 4s electron and two 3d electrons.
- So Cr3+ has d3 configuration.
For [Ni(CN)4]2−:
- CN− is a −1 ligand. Four CN⁻ give −4 charge.
- Overall complex charge is −2, so Ni must be in +2 oxidation state.
- Ni atomic number = 28. Configuration: [Ar]3d84s2.
- Ni2+ loses the two 4s electrons → d8 configuration.
Always remember: in transition metal ions, the 4s electrons are lost before the 3d electrons when forming cations.
2. Identify the geometry and crystal field splitting pattern
[Cr(NH3)6]3+ — six ligands → octahedral geometry.
- In octahedral field, d-orbitals split into:
- Lower energy: t2g (dxy,dxz,dyz) — three orbitals
- Higher energy: eg (dx2−y2,dz2) — two orbitals
- Splitting energy = Δo
[Ni(CN)4]2− — four ligands, and CN⁻ is a very strong field ligand → square planar geometry.
- Square planar is derived from octahedral by removing two ligands along the z-axis.
- The d-orbital splitting in square planar (energy increasing) is:
- Lowest: dxz,dyz (degenerate)
- Then: dz2
- Then: dxy
- Highest: dx2−y2
- The splitting between the lowest and highest is very large — much larger than Δo for the same ligand.
Crystal field splitting order (energy increasing):
- Octahedral: t2g<eg
- Square planar: dxz=dyz<dz2<dxy<dx2−y2
3. Classify the ligand as weak or strong field
NH3 is a moderate field ligand — it lies in the middle of the spectrochemical series. For Cr3+ (d3), the pairing energy is relatively high because all three electrons are in different orbitals anyway. So even with NH₃, the field is effectively weak for this configuration — no pairing occurs.
CN− is a very strong field ligand — near the top of the spectrochemical series. It causes large splitting, so Δ is much larger than P. This forces maximum pairing.
A quick memory aid: The spectrochemical series from weak to strong — I < Br < Cl < F < OH < H₂O < NH₃ < en < NO₂⁻ < CN⁻ < CO. Anything to the right of NH₃ tends to be strong field for most ions.
4. Fill the d-orbitals and count unpaired electrons …
Method: Crystal Field Theory (CFT) + Electronic Configuration Analysis
This method explains magnetic behaviour by examining:
- The oxidation state of the central metal ion
- Its d-electron count
- The crystal field splitting caused by the ligand
- Whether unpaired electrons remain (paramagnetic) or all electrons are paired (diamagnetic)
Step 1: Determine oxidation state and d-electron count for each complex
For [Cr(NH3)6]3+:
- Ligand: NH3 is neutral → charge on complex = +3 comes from Cr
- So, Cr is in +3 oxidation state
- Cr atomic number = 24 → Cr3+ = [Ar]3d3
- d-electron count = 3
For [Ni(CN)4]2−:
- Ligand: CN− has charge –1; four ligands give –4
- Complex charge = –2 → Ni must be in +2 oxidation state
- Ni atomic number = 28 → Ni2+ = [Ar]3d8
- d-electron count = 8
Step 2: Identify ligand field strength and geometry
| Complex | Ligand | Field strength | Geometry |
|---|---|---|---|
| [Cr(NH3)6]3+ | NH3 | Moderate field (irrelevant for d3 — no pairing choice exists) | Octahedral |
| [Ni(CN)4]2− | CN− | Strong field (low spin) | Square planar |
Key fact: CN− is a strong field ligand that causes large splitting; NH3 is intermediate — and for Cr3+ (d3) the distinction does not matter, since three electrons occupy the three t2g orbitals singly under any field strength.
Step 3: Fill d-orbitals according to Hund’s rule and splitting
For [Cr(NH3)6]3+ (octahedral, d3):
- Octahedral splitting: t2g (lower energy) and eg (higher energy)
- With 3 electrons: all go into t2g unpaired (Hund’s rule)
- Unpaired electrons = 3 → Paramagnetic
For [Ni(CN)4]2− (square planar, d8): …
Here’s a breakdown of the common mistakes students make on this exact question, and how to avoid each one.
Mistake 1: Forgetting to find the oxidation state of the metal first
Students often jump straight to the electronic configuration of the neutral atom (Cr or Ni) without adjusting for the charge on the complex.
- Why it’s wrong: The number of electrons on the metal changes when it forms a complex. You must know the exact dn configuration of the metal ion inside the complex.
- How to avoid: Always calculate the oxidation state of the metal first.
- For [Cr(NH3)6]3+: NH3 is neutral. Let Cr be x. x+6(0)=+3⟹x=+3. So, Cr is in +3 state.
- For [Ni(CN)4]2−: CN− has a -1 charge. Let Ni be x. x+4(−1)=−2⟹x=+2. So, Ni is in +2 state.
Mistake 2: Using the wrong electronic configuration for the ion
Once you have the oxidation state, students often write the configuration of the neutral atom and then remove electrons from the wrong orbitals (e.g., removing 4s electrons before 3d).
- Why it’s wrong: In transition metal ions, the 4s orbital is higher in energy than the 3d orbital. Electrons are always removed from the 4s orbital first.
- How to avoid: Write the configuration of the neutral atom, then remove the required number of electrons from the 4s orbital first, then the 3d orbital.
- Cr (Z=24): [Ar]3d54s1 (remember the exception for half-filled stability).
- Cr3+: Remove 3 electrons. Remove the 1 from 4s, then 2 from 3d. Result: [Ar]3d3.
- Ni (Z=28): [Ar]3d84s2.
- Ni2+: Remove 2 electrons. Remove both from 4s. Result: [Ar]3d8.
Mistake 3: Ignoring the ligand field strength (the “why” of pairing)
This is the most critical mistake. Students correctly identify the d8 configuration for Ni2+ but then say it must be paramagnetic because d8 has two unpaired electrons in the free ion.
- Why it’s wrong: The magnetic property depends on the geometry and ligand strength. CN− is a strong field ligand that causes pairing.
- How to avoid: Always check the ligand and geometry.
- For [Ni(CN)4]2−: CN− is strong field. The geometry is square planar (common for d8 with strong ligands). In square planar, the energy gap is so large that all 8 electrons pair up. Result: 0 unpaired electrons → Diamagnetic.
- For [Cr(NH3)6]3+: NH3 is a moderate field ligand. The geometry is octahedral. For a d3 configuration, even in a strong field, you cannot pair electrons because you need at least 4 electrons to start pairing (Hund’s rule). Result: 3 unpaired electrons → Paramagnetic.
Mistake 4: Confusing “paramagnetic” with “diamagnetic” based on the metal alone …
Showing the 12 most recent of 19 on this concept.
- CBSE 2026Set 56/3/11 markMCQQ.In aqueous solution, Cr2O72− ion converts to which of the following in alkaline medium ? (A) Cr3+ (B) CrO42− (C) CrO (D) CrO3
›Reveal solutionSolution
In alkaline medium, dichromate (Cr2O72−) converts to chromate (CrO42−) without any change in oxidation state — it’s a simple acid-base equilibrium, not a redox reaction. The correct option is (B).
The key to this question lies in understanding that the conversion of dichromate to chromate is not a redox reaction — the oxidation state of chromium remains +6 throughout. Many students instinctively think of reduction to Cr3+ because they associate dichromate with strong oxidizing behaviour, but that only happens in acidic medium. In alkaline conditions, the chemistry is entirely different.
Let’s walk through the reasoning step by step.
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Recall the oxidation state of chromium in dichromate.
In Cr2O72−, each oxygen is -2, so total from seven oxygens is -14. The ion has a -2 charge, so the sum of oxidation states of the two chromium atoms must be +12. Hence each Cr is in the +6 state.
-
Now consider the alkaline medium.
When you add a base (like NaOH) to a solution of K2Cr2O7, the dichromate ion reacts with hydroxide ions. The reaction is:
Cr2O72−+2OH−→2CrO42−+H2O
Notice that the oxidation state of Cr in CrO42− is also +6 (four oxygens at -2 give -8, charge -2, so Cr = +6). No electrons are transferred — this is an acid-base equilibrium, not a redox change.
- Why does this happen? Dichromate exists in equilibrium with chromate, and the position depends on pH. In acidic solution, the equilibrium shifts toward dichromate; in alkaline solution, it shifts toward chromate. The reaction is:
2CrO42−+2H+⇌Cr2O72−+H2O
Adding OH− removes H+, pulling the equilibrium to the left — producing chromate. …
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- CBSE 2026Set 56/1/11 markMCQQ.Assertion (A) : Actinoids show wide range of oxidation states. Reason (R) : Actinoids are radioactive in nature. (A) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A). (B) Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of the Assertion (A). (C) Assertion (A) is true, but Reason (R) is false. (D) Assertion (A) is false, but Reason (R) is true.
›Reveal solutionSolution
The assertion that actinoids show a wide range of oxidation states is true, but the reason given — that they are radioactive — is not the correct explanation. The correct explanation lies in the small energy gap between 5f, 6d, and 7s orbitals, which allows many electrons to participate in bonding. So the answer is option (B).
The question tests your understanding of why actinoids (elements 90–103, from thorium to lawrencium) exhibit so many different oxidation states. Many students memorise that “actinoids show variable oxidation states” and also know they are radioactive, so they assume the second explains the first. That’s a trap.
Let’s break it down properly.
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Is Assertion (A) true?
Yes. Actinoids display a remarkably wide range of oxidation states. For example, uranium shows +3, +4, +5, and +6; neptunium and plutonium go from +3 to +7. This is far more varied than most d-block elements. The reason is that the 5f, 6d, and 7s orbitals are very close in energy. Electrons from all three can be lost with relatively little energy cost, so many different oxidation numbers become accessible.
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Is Reason (R) true?
Yes, actinoids are indeed radioactive. All actinoid nuclei are unstable and decay over time. So the reason statement is factually correct.
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Does the radioactivity explain the wide range of oxidation states?
No. Radioactivity is a nuclear property — it depends on the instability of the nucleus (proton/neutron ratio, nuclear binding energy). Oxidation states are an electronic property — they depend on how easily electrons are lost from the outer orbitals. These two phenomena are completely independent.
Watch outA common mistake is to think that because both statements are true, the reason must be the explanation. But correlation is not causation. Radioactivity does not cause variable oxidation states; the orbital energy structure does.
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What actually causes the wide range of oxidation states in actinoids? …
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- CBSE 2026Set ANNUAL1 markMCQQ.Which of the following oxidation states is common for all lanthanoids?(a) +2(b) +3(c) +4(d) +5
›Reveal solutionSolution
All lanthanoids show a characteristic +3 oxidation state because it corresponds to a stable, similar electronic configuration achieved after losing the two 6s and one 4f (or 5d) electron.
Lanthanoids have the general electronic configuration [Xe] 4f^(1-14) 5d^(0-1) 6s2. Removal of the two 6s electrons and one more electron (from 4f or 5d) gives the Ln3+ ion, which is the most stable and commonly observed oxidation state across the entire series, from Ce to Lu.
…
- CBSE 2025Set 56/4/11 markMCQQ.The product of the oxidation of I− with MnO4− in alkaline medium is : (A) IO4− (B) I2 (C) IO− (D) IO3−
›Reveal solutionSolution
In alkaline medium, permanganate (MnO4−) oxidises iodide (I−) to iodate (IO3−), not to iodine or periodate. The balanced reaction shows I− loses 6 electrons to form IO3−, while MnO4− gains 3 electrons to form MnO2. The correct product is IO3−, option (D).
Why the medium matters
The oxidation state of iodine in its products depends heavily on the pH of the solution. Permanganate is a powerful oxidising agent, but its reduction product changes with medium:
- In acidic medium: MnO4−→Mn2+ (gains 5 electrons)
- In neutral/alkaline medium: MnO4−→MnO2 (gains 3 electrons)
This difference in electron gain per mole of permanganate directly affects how far it can oxidise iodide. In alkaline medium, permanganate is a milder oxidising agent (gains only 3 electrons) compared to acidic medium (gains 5 electrons). Yet it still oxidises I− all the way to IO3−, not stopping at I2.
Step-by-step reasoning
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Identify the half-reactions
Iodide (I−) has oxidation state −1. The possible products given are:
- IO4−: iodine in +7 state
- I2: iodine in 0 state
- IO−: iodine in +1 state (hypoiodite)
- IO3−: iodine in +5 state (iodate)
In alkaline medium, permanganate reduces to MnO2 (manganese in +4 state, from +7 in MnO4−).
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Balance the oxidation half-reaction
Iodide going to iodate:
I−→IO3−
Balance oxygen with water (alkaline medium):
I−+3H2O→IO3−+6H+
Balance charge: left side has −1, right side has −1+6=+5. Add 6 electrons to right:
I−+3H2O→IO3−+6H++6e−
In alkaline medium, add OH− to neutralise H+:
I−+6OH−→IO3−+3H2O+6e−
So each I− loses 6 electrons to become IO3−.
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Balance the reduction half-reaction
Permanganate to manganese dioxide in alkaline medium:
MnO4−→MnO2
Balance oxygen with water:
MnO4−+2H2O→MnO2+4OH−
Balance charge: left −1, right −4. Add 3 electrons to left:
MnO4−+2H2O+3e−→MnO2+4OH−
So each MnO4− gains 3 electrons.
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Combine the half-reactions
To equalise electrons: multiply reduction half by 2 (gives 6 electrons gained) and oxidation half by 1 (gives 6 electrons lost):
2MnO4−+4H2O+6e−→2MnO2+8OH−
I−+6OH−→IO3−+3H2O+6e−
Adding:
2MnO4−+I−+4H2O+6OH−→2MnO2+IO3−+3H2O+8OH−
Cancel 3H2O from both sides and 6OH− from both sides: …
- CBSE 2025Set 56/6/11 markMCQQ.For the following question, two statements are given — one labelled as Assertion (A) and the other labelled as Reason (R). Select the correct answer from the codes (A), (B), (C) and (D) as given below. (A) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A). (B) Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of the Assertion (A). (C) Assertion (A) is true, but Reason (R) is false. (D) Assertion (A) is false, but Reason (R) is true. Assertion (A) : Actinoids show wide range of oxidation states. Reason (R) : Actinoids are radioactive in nature.
›Reveal solutionSolution
The assertion that actinoids show a wide range of oxidation states is true, but the reason given — that they are radioactive — does not explain this property. The correct answer is (B).
The question tests your understanding of why actinoids exhibit variable oxidation states. The key is to separate two distinct facts: actinoids are radioactive, and they do show many oxidation states — but the radioactivity is not the cause of the oxidation state variability.
Let’s break this down.
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Why do actinoids show a wide range of oxidation states?
The 5f, 6d, and 7s orbitals in actinoids are very close in energy. This means electrons can be removed from any of these orbitals with relatively little energy cost. As you move across the actinoid series, the 5f orbitals gradually become more stable, but early actinoids (like Th, Pa, U, Np, Pu) can lose anywhere from 3 to 7 electrons. For example, uranium shows +3, +4, +5, and +6; plutonium shows +3, +4, +5, +6, and +7. This is the real reason for the wide range — it’s an electronic structure effect, not a nuclear one.
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What about radioactivity?
Yes, all actinoids are radioactive — their nuclei are unstable and decay over time. But radioactivity is a nuclear property, while oxidation states depend on electron configuration. A nucleus decaying does not directly change how many electrons an atom can lose or gain in a chemical reaction. So while both statements are factually true, the reason does not explain the assertion. …
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- CBSE 2025Set ANNUAL1 markQ.What is the common oxidation state of Lanthanoids?
›Reveal solutionSolution
All lanthanoids overwhelmingly favour the +3 oxidation state, since their poorly-bonding 4f electrons are not readily involved, leaving the same outer 5d/6s electrons available across the series.
Across the entire lanthanide series, the +3 oxidation state is by far the most common and stable one, shown by essentially every lanthanoid. This is because the 4f electrons are deeply buried and well-shielded, taking little part in bonding, while the outer 5d0−16s2 electrons are readily lost to give the stable Ln3+ ion. Occasional +2 or +4 states occur only for a few elements whe …
- CBSE 2024Set A11 markMCQQ.Which of the following pair of metal oxides are amphoteric?(a) V2O5, Cr2O3(b) Mn2O7, CrO3(c) V2O5, V2O4(d) CrO, V2O5
›Reveal solutionSolution
V2O5 and Cr2O3 are the amphoteric pair — option (a).
For transition-metal oxides, the character changes from basic (low oxidation state) through amphoteric to acidic (high oxidation state). Cr2O3 (Cr in +3) is amphoteric — it dissolves in acids to give Cr3+ salts and in alkali to give chromite. V2O5 (V in +5) is chiefly acidic but is genuinely amphoteric, dissolving in both acids and alka …
- CBSE 2024Set ANNUAL1 markMCQQ.Which of the following oxidation state is common for all lanthanoids ?(a) +2(b) +3(c) +4(d) +5
›Reveal solutionSolution
Every lanthanoid shows the +3 oxidation state as its characteristic and most stable state, even though a few also show +2 or +4 in special cases.
Lanthanoids (Ce to Lu) have the general electronic configuration [Xe]4f1−145d0−16s2. Losing the two 6s electrons and one 4f/5d electron gives the stable, half-filled/fully-filled-favouring Ln3+ ion, which is why +3 is the predominant and universally shown oxidation state across the whole series. A handful of lanthanoids additi …
- CBSE 2023Set 56/1/11 markMCQQ.The most common and stable oxidation state of a Lanthanoid is : (A) + 2 (B) + 3 (C) + 4 (D) + 6
›Reveal solutionSolution
Lanthanoids overwhelmingly prefer the +3 oxidation state due to the stability gained from losing the two 6s and one 5d/4f electron, achieving a configuration analogous to noble gases or half-filled/filled f-subshells. The answer is (B) +3.
Why Lanthanoids Love +3: Electronic Configuration and Stability
The lanthanoid series (elements 57–71: La through Lu) sits in the f-block, where the 4f orbitals are being progressively filled. To understand their oxidation state preference, we need to look at what electrons are available and what configurations become stable upon ionization.
A typical lanthanoid has the general electronic configuration:
[Xe]4f0−145d0−16s2
The 6s electrons are outermost and easiest to remove. The 5d and 4f orbitals are close in energy, so sometimes one electron occupies 5d instead of 4f. When a lanthanoid forms a cation, it loses electrons in a specific order: 6s electrons go first, then 5d, then 4f (because 4f is more tightly held, being an inner orbital).
Step-by-Step Reasoning
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First ionization removes 6s electrons
All lanthanoids have two 6s electrons. Removing both gives a +2 state, but this is rarely the stopping point because the resulting ion still has relatively accessible 5d or 4f electrons.
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Third electron removal: the key to +3 stability
After losing the two 6s electrons, removing one more electron (from 5d if occupied, otherwise from 4f) produces the +3 oxidation state. This configuration turns out to be remarkably stable across the entire series.
Why? The resulting Ln3+ ion achieves one of several favorable electronic arrangements:
- For La (4f0): [Xe] — a noble gas configuration.
- For Gd (4f7): half-filled f-subshell with all spins parallel (exchange energy stabilization).
- For Lu (4f14): completely filled f-subshell.
- For others: partially filled 4f with reasonable stability.
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Why not +2?
The +2 state does exist for a few lanthanoids (Eu, Yb) where it leads to half-filled or filled f-subshells (4f7 for Eu²⁺, 4f14 for Yb²⁺), but these are exceptions, not the rule. Most lanthanoids find +2 too reducing and unstable in aqueous solution.
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Why not +4 or higher?
Removing a fourth electron means breaking into the tightly held 4f subshell (which is shielded and contracted). The ionization energy jumps dramatically. Only Ce commonly shows +4 (because Ce⁴⁺ achieves 4f0=[Xe]), and even that is a strong oxidizing agent. Higher states like +6 are virtually unknown in lanthanoids—the 4f electrons are too stable to remove. …
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- CBSE 2023Set 56/2/11 markMCQQ.The oxidation state of Fe in [Fe(CO)5] is (A) +2 (B) 0 (C) +3 (D) +5
›Reveal solutionSolution
Carbonyl (CO) is a neutral ligand that does not contribute any charge. With five neutral CO ligands, the overall complex is neutral, so Fe must be in the 0 oxidation state. The correct option is (B).
Why this is a trick question — and how to see through it
Most students memorise that transition metals in coordination compounds usually show positive oxidation states like +2 or +3. Iron especially is famous for Fe(II) and Fe(III). So when you see
[Fe(CO)5], the instinct is to guess +2 or +3. That instinct is wrong here — and the reason is beautiful.The key is to ask: What charge does each ligand bring?
CO (carbonyl) is a neutral ligand. It donates a lone pair to the metal but carries no net charge. If every ligand is neutral, and the overall complex is neutral (no square brackets with a superscript charge), then the metal must be in the zero oxidation state.
This is not a rare exception — it is a whole class of compounds called metal carbonyls, where metals often exist in low or zero oxidation states. CO is a strong field ligand that stabilises these low states through back-bonding.
Step-by-step reasoning
1. Identify the charge on each ligand.
CO is carbon monoxide — a neutral molecule. In coordination chemistry, neutral ligands contribute 0 to the oxidation state calculation. Other examples: NH₃, H₂O, PPh₃.
2. Identify the overall charge on the complex.
The formula is written as
[Fe(CO)5]— no superscript charge. That means the complex is neutral: overall charge = 0.3. Set up the oxidation state equation.
Let the oxidation state of Fe be x.
Each CO contributes 0. There are 5 CO ligands.
So:
x+5(0)=0
4. Solve for x.
x=0
That is the entire calculation — it takes one line once you know the rule.
Watch outA common mistake is to treat CO as if it were a charged ligand like CN⁻ or Cl⁻. CO is not cyanide — it is neutral. Do not assign it a −1 charge. Also, do not confuse this with ferrocene or other organometallics where the ligand (like cyclopentadienyl) is anionic. …
- CBSE 2023Set 56/2/11 markMCQQ.Which of the following characteristics of transition metals is associated with their catalytic activity ? (A) Paramagnetic nature (B) Colour of hydrated ions (C) High enthalpy of atomisation (D) Variable oxidation states
›Reveal solutionSolution
The catalytic activity of transition metals arises primarily from their ability to adopt variable oxidation states, which allows them to form intermediate complexes and lower activation energy. The correct option is (D).
Why this question tests a core idea
Catalysis is about providing an alternative reaction pathway with a lower activation energy. For a substance to be a good catalyst, it must be able to temporarily bind to reactants, change its own electronic state, and then release the products. Transition metals excel at this because they can change their oxidation state easily — often by ±1 — without breaking down. This flexibility lets them shuttle electrons to and from reactants, stabilising transition states that would otherwise be too high in energy.
The other options — paramagnetism, colour, and high enthalpy of atomisation — are important properties of transition metals, but they don't directly explain catalytic activity. Let's see why.
Step-by-step reasoning
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Paramagnetic nature (A)
Paramagnetism arises from unpaired electrons. While many transition metal ions are paramagnetic, this property has no direct role in catalysis. A catalyst doesn't need unpaired electrons to speed up a reaction — it needs to form bonds with reactants and then break them. Paramagnetism is a consequence of electronic configuration, not a cause of catalytic behaviour.
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Colour of hydrated ions (B)
The colour of transition metal complexes comes from d–d transitions — electrons jumping between split d orbitals when they absorb visible light. This is fascinating, but it's a spectroscopic property. Colour tells us about the electronic structure of the ion, but it doesn't help the ion catalyse a reaction. A colourless catalyst can be just as effective.
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High enthalpy of atomisation (C)
This refers to the energy required to convert a solid metal into isolated gaseous atoms. Transition metals have high enthalpies of atomisation because of strong metallic bonding (due to unpaired d electrons contributing to bonding). This property is related to the strength of the metal lattice, not to its ability to change oxidation states during a catalytic cycle. In fact, a very high enthalpy of atomisation might make it harder for the metal to leave the lattice and participate in solution-phase catalysis.
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Variable oxidation states (D) …
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- CBSE 2023Set ANNUAL1 markMCQQ.Which of the following lanthanoid ions in solution is a good oxidizing agent ?(a) Eu2+(b) Yb2+(c) Sm2+(d) Tb4+
›Reveal solutionSolution
+3 is the overwhelmingly preferred oxidation state across the whole lanthanide series, so an unusual +4 ion like Tb⁴⁺ tends to gain an electron and revert to +3 — making it a good oxidising agent.
Across the lanthanide series, +3 is by far the most stable and common oxidation state (arising from the overall energetics of the whole series, not just an individual ion's own f-subshell configuration). Ions that deviate from +3 — whether to +2 or +4 — tend to revert back to +3, and in doing so they act as either reducing or oxidising agents:
- +2 lanthanide ions (Eu²⁺, Sm²⁺, Yb²⁺) tend to lose an electron to revert to +3 — they act as reducing agents. …
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